High-carbon biogenic reagents and uses thereof

ABSTRACT

This invention provides processes and systems for converting biomass into high-carbon biogenic reagents that are suitable for a variety of commercial applications. Some embodiments employ pyrolysis in the presence of an inert gas to generate hot pyrolyzed solids, condensable vapors, and non-condensable gases, followed by separation of vapors and gases, and cooling of the hot pyrolyzed solids in the presence of the inert gas. Additives may be introduced during processing or combined with the reagent, or both. The biogenic reagent may include at least 70 wt %, 80 wt %, 90 wt %, 95 wt %, or more total carbon on a dry basis. The biogenic reagent may have an energy content of at least 12,000 Btu/lb, 13,000 Btu/lb, 14,000 Btu/lb, or 14,500 Btu/lb on a dry basis. The biogenic reagent may be formed into fine powders, or structural objects. The structural objects may have a structure and/or strength that derive from the feedstock, heat rate, and additives.

PRIORITY DATA

This patent application is a continuation of U.S. patent applicationSer. No. 15/654,262 filed Jul. 19, 2017, which is a divisional of U.S.patent application Ser. No. 14/548,874 filed Nov. 20, 2014 (now U.S.Pat. No. 9,752,090), which is a continuation of U.S. patent applicationSer. No. 13/446,764 filed Apr. 13, 2012 (now U.S. Pat. No. 8,920,525),which claims the priority benefit of U.S. Provisional Patent ApplicationNos. 61/476,025, 61/476,043, 61/475,930, 61/475,937, 61/475,943,61/475,946, 61/475,949, 61/475,956, 61/475,959, 61/475,968, 61/475,971,61/475,973, 61/475,977, 61/475,981, 61/475,991, 61/475,996, 61/476,049,each filed on Apr. 15, 2011, the disclosures of which are herebyincorporated by reference.

FIELD OF THE INVENTION

The present invention generally relates to processes, systems, andapparatus for the production of high-carbon biogenic reagents, andcompositions, products, and uses related thereto.

BACKGROUND OF THE INVENTION

Carbon is a platform element in a wide variety of industries and has avast number of chemical, material, and fuel uses. Carbon is a good fuelto produce energy, including electricity. Carbon also has tremendouschemical value for various commodities and advanced materials, includingmetals, metal alloys, composites, carbon fibers, electrodes, andcatalyst supports. For metal making, carbon is useful as a reactant, forreducing metal oxides to metals during processing; as a fuel, to provideheat for processing; and as a component of the final metal alloy. Carbonis a very important element in steel since it allows steel to behardened by heat treatment.

Carbon-based reagents can be produced, in principle, from virtually anymaterial containing carbon. Carbonaceous materials commonly includefossil resources such as natural gas, petroleum, coal, and lignite; andrenewable resources such as lignocellulosic biomass and variouscarbon-rich waste materials.

Biomass is a term used to describe any biologically produced matter, orbiogenic matter. The chemical energy contained in biomass is derivedfrom solar energy using the natural process of photosynthesis. This isthe process by which plants take in carbon dioxide and water from theirsurroundings and, using energy from sunlight, convert them into sugars,starches, cellulose, hemicellulose, and lignin. Of all the renewableenergy sources, biomass is unique in that it is, effectively, storedsolar energy. Furthermore, biomass is the only renewable source ofcarbon.

By utilizing biogenic carbon for fuel, CO₂ emissions associated with thecombustion do not contribute to net life-cycle carbon emissions becausecarbon is recycled to grow more biomass. Also, use of biogenic carbon asa fuel will typically cause lower emissions of sulfur dioxide andmercury, compared to use of coal or other solid fossil fuels for energyproduction.

For chemical and material applications in which the carbon will not beimmediately combusted, by utilizing biogenic carbon, the carbon can beeffectively sequestered for long periods of time (e.g., when carbon isadded to steel for permanent structures). In this way, the net carbonemissions are actually negative—CO₂ from the atmosphere is used to growbiogenic feedstocks and then the carbon is sequestered in biogenicproducts.

Converting biomass to high-carbon reagents, however, poses bothtechnical as well as economic challenges arising from feedstockvariations, operational difficulties, and capital intensity. There exista variety of conversion technologies to turn biomass feedstocks intohigh-carbon materials. Most of the known conversion technologies utilizesome form of pyrolysis.

Pyrolysis is a process for thermal conversion of solid materials in thecomplete absence of oxidizing agent (air or oxygen), or with suchlimited supply that oxidation does not occur to any appreciable extent.Depending on process conditions and additives, biomass pyrolysis can beadjusted to produce widely varying amounts of gas, liquid, and solid.Lower process temperatures and longer vapor residence times favor theproduction of solids. High temperatures and longer residence timesincrease the biomass conversion to syngas, while moderate temperaturesand short vapor residence times are generally optimum for producingliquids. Recently, there has been much attention devoted to pyrolysisand related processes for converting biomass into high-quality syngasand/or to liquids as precursors to liquid fuels.

On the other hand, there has been less focus on improving pyrolysisprocesses specifically for optimizing yield and quality of the solids ashigh-carbon reagents. Historically, slow pyrolysis of wood has beenperformed in large piles, in a simple batch process, with no emissionscontrol. Traditional charcoal-making technologies are energy-inefficientas well as highly polluting. Clearly, there are economic and practicalchallenges to scaling up such a process for continuous commercial-scaleproduction of high-quality carbon, while managing the energy balance andcontrolling emissions.

SUMMARY OF THE INVENTION

In some variations, the present invention provides a process forproducing a high-carbon biogenic reagent, the process comprising:

(a) providing a carbon-containing feedstock comprising biomass;

(b) optionally drying the feedstock to remove at least a portion ofmoisture contained within the feedstock;

(c) optionally deaerating the feedstock or the dried feedstock to removeat least a portion of interstitial oxygen, if any, contained with thefeedstock;

(d) in a pyrolysis zone, pyrolyzing the feedstock in the presence of asubstantially inert gas for at least about 10 minutes and with apyrolysis temperature selected from about 250° C. to about 700° C., togenerate hot pyrolyzed solids, condensable vapors, and non-condensablegases;

(e) separating at least a portion of the condensable vapors and at leasta portion of the non-condensable gases from the hot pyrolyzed solids;

(f) in a cooling zone, cooling the hot pyrolyzed solids, in the presenceof the substantially inert gas for at least about 5 minutes and with acooling-zone temperature less than the pyrolysis temperature, togenerate warm pyrolyzed solids;

(g) in an optional cooler that is separate from the cooling zone,further cooling the warm pyrolyzed solids to generate cool pyrolyzedsolids; and

(h) recovering a high-carbon biogenic reagent comprising at least aportion of the warm or cool pyrolyzed solids.

The term “reactor” herein refers to a discrete unit in which atmosphericand temperature conditions can be controlled and in which a physicaland/or chemical reaction can take place. The term “zone” in the presentcontext refers to an area within a reactor in which temperatureconditions and atmospheric conditions can be controlled relative toother zones within the reactor.

The term “biomass processing unit” herein refers to a reactor thatincludes a plurality of zones as discussed in more detail below. Invarious embodiments, the biomass processing unit (“BPU”) includes aplurality of output passageways configured to transfer the raw materialor feedstock at different stages of processing, gases, condensatebyproducts, and heat from various reactors and zones to any one or moreof the other reactors or zones, the material feed system, the carbonrecovery unit, and any other contemplated components of the systemdescribed herein. In one embodiment, after the raw material has passedthrough each of the zones of the BPU, the raw material is carbonized.

The term “carbonization” herein means increasing the carbon content in agiven amount of biomass. Carbonization can illustratively beaccomplished by reducing non-carbon containing material from thebiomass, adding carbon atoms to the biomass or both to form a“high-carbon biogenic reagent.”

As discussed below, various multi-zone BPU embodiments include a singlereactor and various multi-zone BPU embodiments could also include morethan one separate reactor. It should be appreciated that otherembodiments discussed below include multiple separate reactors, eachreactor having at least one zone. For the purposes of this disclosure,the properties, principles, processes, alternatives, and embodimentsdiscussed with respect to all single reactor multi-zone BPU embodimentsapply equally to all multiple separate reactor embodiments, andvice-versa.

In some embodiments, the process comprises drying the feedstock toremove at least a portion of moisture contained within the feedstock. Inthese or other embodiments, the process comprises deaerating thefeedstock to remove at least a portion of interstitial oxygen containedwith the feedstock.

The process may further include preheating the feedstock, prior to step(d), in a preheating zone in the presence of the substantially inert gasfor at least 5 minutes and with a preheating temperature selected fromabout 80° C. to about 500° C., or from about 300° C. to about 400° C.

In some embodiments, the pyrolysis temperature is selected from about400° C. to about 600° C. In some embodiments, pyrolysis in step (d) iscarried out for at least 20 minutes. The cooling-zone temperature may beselected from about 150° C. to about 350° C., for example.

Pyrolysis conditions may be selected to maintain the structuralintegrity or mechanical strength of the high-carbon biogenic reagentrelative to the feedstock, when it is desired to do so for a certainproduct application.

In some embodiments, each of the zones is located within a singlereactor or a BPU. In other embodiments, each of the zones is located inseparate BPUs or reactors. It should be appreciated that someembodiments include one or more BPUs, each including at least one zone.

The substantially inert gas may be selected from the group consisting ofN₂, Ar, CO, CO₂, H₂, CH₄, and combinations thereof. Some of thesubstantially inert gas may include one or more non-condensable gasspecies (e.g., CO and CO₂) recycled from step (e). In some embodiments,the pyrolysis zone and the cooling zone each comprise a gas phasecontaining less than 5 wt % oxygen, such as about 1 wt % oxygen or less.

The process may be continuous, semi-continuous, or batch. In somecontinuous or semi-continuous embodiments, the inert gas flowssubstantially countercurrent relative to the direction of solids flow.In other continuous or semi-continuous embodiments, the inert gas flowssubstantially cocurrent relative to the direction of solids flow.

In some embodiments, the process includes monitoring and controlling theprocess with at least one reaction gas probe, such as two or morereaction gas probes. Monitoring and controlling the process can improveprocess energy efficiency. Monitoring and controlling the process canalso improve a product attribute associated with the high-carbonbiogenic reagent, such as (but not limited to) carbon content, energycontent, structural integrity, or mechanical strength.

The process may further include thermal oxidation (i.e., combustion) ofat least a portion of the condensable and non-condensable vapors with anoxygen-containing gas. The thermal oxidation may be assisted withcombustion of natural gas. Heat produced from the thermal oxidation maybe utilized, at least in part, for drying the feedstock. Additionally,heat produced from the thermal oxidation may be utilized, at least inpart, to heat the substantially inert gas before entering one of thezones or reactors, such as the pyrolysis zone.

The process may further include combining at least a portion of thevapors with the cooled pyrolyzed solids, to increase the carbon contentof the high-carbon biogenic reagent. Alternatively, or additionally, theprocess may further include combining at least a portion of thecondensable vapors with the warm pyrolyzed solids, to increase thecarbon content of the high-carbon biogenic reagent.

Condensable vapors may thus be used for either energy in the process(such as by thermal oxidation) or in carbon enrichment, to increase thecarbon content of the high-carbon biogenic reagent. Certainnon-condensable gases, such as CO or CH₄, may be utilized either forenergy in the process, or as part of the substantially inert gas for thepyrolysis step.

In some embodiments, the process further comprises introducing at leastone additive selected from acids, bases, or salts thereof. The additivemay be selected from (but not limited to) the group consisting of sodiumhydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide,hydrogen chloride, sodium silicate, potassium permanganate, andcombinations thereof.

In some embodiments, the process further comprises introducing at leastone additive selected from the group consisting of a metal, a metaloxide, a metal hydroxide, a metal halide, and combinations thereof. Theadditive may be selected from (but not limited to) the group consistingof magnesium, manganese, aluminum, nickel, chromium, silicon, boron,cerium, molybdenum, phosphorus, tungsten, vanadium, iron halide, ironchloride, iron bromide, magnesium oxide, dolomite, dolomitic lime,fluorite, fluorospar, bentonite, calcium oxide, lime, and combinationsthereof.

Additives may be added before, during, or after any one or more steps ofthe process, including into the feedstock itself at any time, before orafter it is harvested. Additives may be introduced prior to or duringstep (b), prior to or during step (d), during step (f), during step (g),between steps (f) and (g), or after step (g), for example. An additivemay be introduced to the warm pyrolyzed solids. For example, an additivemay be introduced in an aqueous solution, vapor, or aerosol to assistwith cooling of the warm pyrolyzed solids in step (g). In these or otherembodiments, an additive is introduced to the cool pyrolyzed solids toform the high-carbon biogenic reagent containing the additive.

In some embodiments, the process further comprises introducing at leasta portion of the cool pyrolyzed solids to a separate unit for additionalpyrolysis, in the presence of a substantially inert gas for at leastabout 30 minutes and with a pyrolysis temperature selected from about200° C. to about 600° C., to generate a solid product having highercarbon content than the cool pyrolyzed solids.

In some embodiments, the process further comprises operating a cooler tocool the warm pyrolyzed solids with steam, thereby generating the coolpyrolyzed solids and superheated steam; wherein the drying is carriedout, at least in part, with the superheated steam derived from theexternal cooler. Optionally, the cooler may be operated to first coolthe warm pyrolyzed solids with steam to reach a first coolertemperature, and then with air to reach a second cooler temperature,wherein the second cooler temperature is lower than the first coolertemperature and is associated with a reduced combustion risk for thewarm pyrolyzed solids in the presence of the air.

In some variations, the invention provides a process for producing ahigh-carbon biogenic reagent, the process comprising:

(a) providing a carbon-containing feedstock comprising biomass(optionally with some or all moisture removed);

(b) in a pyrolysis zone, pyrolyzing the feedstock in the presence of asubstantially inert gas for at least 10 minutes and with a pyrolysistemperature selected from about 250° C. to about 700° C., to generatehot pyrolyzed solids, condensable vapors, and non-condensable gases;

(c) separating at least a portion of the condensable vapors and at leasta portion of the non-condensable gases from the hot pyrolyzed solids;

(d) in a cooling zone, cooling the hot pyrolyzed solids, in the presenceof the substantially inert gas for at least about 5 minutes and with acooling temperature less than the pyrolysis temperature, to generatewarm pyrolyzed solids;

(e) in an optional cooler that is separate from the cooling zone,further cooling the warm pyrolyzed solids to generate cool pyrolyzedsolids; and

(f) recovering a high-carbon biogenic reagent comprising at least aportion of the warm or cool pyrolyzed solids.

In some variations, the invention provides a process for producing ahigh-carbon biogenic reagent, the process comprising:

(a) providing a carbon-containing feedstock comprising biomass;

(b) optionally drying the feedstock to remove at least a portion ofmoisture, if any, contained within the feedstock;

(c) optionally deaerating the feedstock to remove at least a portion ofinterstitial oxygen, if any, contained with the feedstock;

(d) in a preheating zone, preheating the feedstock in the presence of asubstantially inert gas for at least about 5 minutes and with apreheating temperature selected from about 80° C. to about 500° C.;

(e) in a pyrolysis zone, pyrolyzing the feedstock in the presence of asubstantially inert gas for at least about 10 minutes and with apyrolysis temperature selected from about 250° C. to about 700° C., togenerate hot pyrolyzed solids, condensable vapors, and non-condensablegases;

(f) separating at least a portion of the condensable vapors and at leasta portion of the non-condensable gases from the hot pyrolyzed solids;

(g) in a cooling zone, cooling the hot pyrolyzed solids, in the presenceof a substantially inert gas for at least 5 minutes and with a coolingtemperature less than the pyrolysis temperature, to generate warmpyrolyzed solids;

(h) in an optional cooler that is separate from the cooling zone,cooling the warm pyrolyzed solids to generate cool pyrolyzed solids; and

(i) recovering a high-carbon biogenic reagent comprising at least aportion of the warm or cool pyrolyzed solids,

the process further comprising introducing at least one additivesomewhere in the process (i.e., at any one or more locations or times).

In some variations, the invention provides a process for producing ahigh-carbon biogenic reagent, the process comprising:

(a) providing a carbon-containing feedstock comprising biomass;

(b) optionally drying said feedstock to remove at least a portion ofmoisture contained within said feedstock;

(c) optionally deaerating said feedstock to remove at least a portion ofinterstitial oxygen, if any, contained with said feedstock or said driedfeedstock;

(d) in a pyrolysis zone, pyrolyzing said feedstock in the presence of asubstantially inert gas for at least about 10 minutes and with apyrolysis temperature selected from about 250° C. to about 700° C., togenerate hot pyrolyzed solids, condensable vapors, and non-condensablegases;

(e) separating at least a portion of said condensable vapors and atleast a portion of said non-condensable gases from said hot pyrolyzedsolids;

(f) in an optional cooling zone, further cooling said hot pyrolyzedsolids, in the presence of said substantially inert gas for at least 5minutes and with a cooling-zone temperature less than said pyrolysistemperature, to generate warm pyrolyzed solids;

(g) in a cooler that is separate from said cooling zone, cooling saidwarm or cool pyrolyzed solids to generate cool pyrolyzed solids;

(h) recovering a high-carbon biogenic reagent comprising at least aportion of said cool pyrolyzed solids; and

(i) forming a fine powder from said high-carbon biogenic reagent,wherein the process optionally includes introducing at least oneadditive to the process prior to step (i), during step (i), or afterstep (i).

The high-carbon biogenic reagent may contain at least 35% of the carboncontained in the feedstock, such as at least 50% or at least 70% of thecarbon contained in the feedstock. In some embodiments, the high-carbonbiogenic reagent contains between about 40% and about 70% of the carboncontained in the feedstock.

In certain embodiments, an additive is introduced to the dried feedstockprior to or during step (d), and wherein the presence of the additive inthe process increases the carbon content of the high-carbon biogenicreagent compared to an otherwise-identical process without introductionof the additive.

The high-carbon biogenic reagent may contain at least 55 wt % carbon ona dry basis, such as at least 55 wt. %, 60 wt. %, 65 wt. %, 70 wt. %, 75wt. %, 80 wt %, 90 wt %, 95 wt %, or more carbon on a dry basis. Thetotal carbon includes fixed carbon and may also include carbon fromvolatile matter. In some embodiments, the high-carbon biogenic reagentcontains at least 90 wt % or at least 95 wt % fixed carbon on a drybasis.

The high-carbon biogenic reagent may have an energy content of at least11,000 Btu/lb on a dry basis, such as at least 12,000 Btu/lb, at least13,000 Btu/lb, at least 14,000 Btu/lb, at least 14,500 Btu/lb, or atleast 14,700 Btu/lb on a dry basis.

The high-carbon biogenic reagent may be formed into a fine powder byparticle-size reduction. Alternatively, or sequentially, the high-carbonbiogenic reagent may be formed into a structural object by pressing,binding, pelletizing, or agglomeration. In some embodiments, thehigh-carbon biogenic reagent is in the form of structural objects whosestructure and/or strength substantially derive from the feedstock. Incertain embodiments, the high-carbon biogenic reagent is insubstantially the same structural form as the feedstock.

Other variations of the present invention provide a high-carbon biogenicreagent production system, the system comprising:

(a) a material feed system configured to introduce a carbon-containingfeedstock;

(b) an optional dryer, disposed in operable communication with thematerial feed system, configured to remove moisture contained within acarbon-containing feedstock;

(c) a biomass processing unit, disposed in operable communication withthe material feed system or the dryer (if present), wherein the biomassprocessing unit contains at least one pyrolysis zone disposed inoperable communication with a spatially separated cooling zone, andwherein the biomass processing unit is configured with an outlet toremove condensable vapors and non-condensable gases from solids;

(d) a cooler, disposed in operable communication with the biomassprocessing unit; and

(e) a high-carbon biogenic reagent recovery unit, disposed in operablecommunication with the cooler.

The dryer, if present, may be configured as a drying zone within theBPU. In some embodiments, the system further comprises a purging systemfor removing oxygen from the system. The purging system may comprise oneor more inlets to introduce a substantially inert gas, and one or moreoutlets to remove the substantially inert gas and displaced oxygen fromthe system. The purging system may be a deaerater disposed between thematerial feed system (or the dryer, if present) and the BPU.

Optionally, the system may include a preheating zone, disposed inoperable communication with the pyrolysis zone.

Each of the at least one pyrolysis zone, the cooling zone, and thepreheating zone (if present) may be located within a single unit, or inseparate units. The material feed system may be physically integratedwith the BPU. In some embodiments, the cooler is disposed within theBPU.

The system may further include one or more additive feeders forintroducing additive(s) into the system, such as any of theabove-described additives. In some embodiments, an additive feeder isconfigured to combine the additive with the carbon-containing feedstock.An additive feeder may be interposed between the material feed system(for biomass) and the BPU. An additive feeder may be disposed inoperable communication with the BPU. An additive feeder may be disposedin operable communication with the cooler. An additive feeder may beinterposed between the cooler and the carbon recovery unit. An additivefeeder may disposed in operable communication with the carbon recoveryunit, including downstream of the recovery unit itself.

The BPU may be configured with a first gas inlet and a first gas outlet.The first gas inlet and the first gas outlet may be disposed incommunication with different zones, or the same zone. In variousembodiments, the BPU is configured with any one or more of a second gasinlet, a second gas outlet, a third gas inlet, a third gas outlet, afourth gas inlet, and a fourth gas outlet. Optionally, each zone presentin the BPU is configured with a gas inlet and a gas outlet. Gas inletsand outlets allow not only introduction and withdrawal of vapor or gas,but also allow precise process monitoring and control across variousstages of the process, resulting in yield and efficiency improvements.

In some embodiments, the cooling zone is configured with a gas inlet,and the pyrolysis zone is configured with a gas outlet, to generatesubstantially countercurrent flow of the gas phase relative to the solidphase (e.g., the feedstock). In other embodiments, the cooling zone isconfigured with a gas inlet, and the preheating zone is configured witha gas outlet, to generate substantially countercurrent flow of the gasphase relative to the solid phase. In these or other embodiments, thecooling zone is configured with a gas inlet, and the drying zone isconfigured with a gas outlet, to generate substantially countercurrentflow of the gas phase relative to the solid phase.

The system may further comprise a first reaction gas probe disposed inoperable communication with the pyrolysis zone and with a gas-monitoringdevice, such as (but not limited to) GC, MS, GC-MS, or FTIR. In someembodiments, the system further comprises a second reaction gas probedisposed in operable communication with the cooling zone and with thegas-monitoring device or a second gas-monitoring device which may be adifferent type of instrument. The system may include additional reactiongas probes disposed in operable communication with the drying zone (ifpresent) and/or the preheating zone (if present), and with agas-monitoring device. When reaction gas probes are included, the systemmay further include at least one computer-programmed controllerexecutable to utilize output from the gas-monitoring device to adjust asystem set point (such as pyrolysis temperature or inert gas flow rate).

In some embodiments, the system further comprises a process gas heaterdisposed in operable communication with the outlet to remove condensablevapors and non-condensable gases, wherein the process gas heater isconfigured to introduce a separate fuel and an oxidant into a combustionchamber, adapted for combustion of the fuel and at least a portion ofthe condensable vapors.

The system may include a heat exchanger disposed between the process gasheater and the dryer, configured to utilize at least some of the heat ofthe combustion for the dryer. Alternatively, or additionally, the systemmay include a heat exchanger disposed between the process gas heater anda gas inlet for the BPU, configured to utilize at least some of the heatof the combustion for preheating a substantially inert gas prior tointroduction into the BPU.

In some embodiments, the system further comprises a carbon-enrichmentunit, disposed in operable communication with the cooler or the BPU,configured for combining vapors, including noncondensable vapors and/orcondensable vapors in fully or at least partially condensed form, withthe solids to increase the carbon content of the high-carbon biogenicreagent obtained from the carbon recovery unit.

In various embodiments, the system is configured for extracting andreusing gases from the BPU and/or extracting and reusing gases from thecarbon recovery unit.

In some embodiments, the system further comprises a separate pyrolysisunit adapted to further pyrolyze the high-carbon biogenic reagent tofurther increase its carbon content.

Other variations provide a high-carbon biogenic reagent productionsystem, the system comprising:

(a) a material feed system configured to introduce a carbon-containingfeedstock;

(b) an optional dryer, disposed in operable communication with thematerial feed system, configured to remove moisture contained within acarbon-containing feedstock;

(c) a preheater, disposed in operable communication with the materialfeed system or the dryer (if present), configured to heat and/or mildlypyrolyze the feedstock;

(d) a pyrolysis reactor, disposed in operable communication with thepreheater, configured to pyrolyze the feedstock;

(e) a cooler, disposed in operable communication with the pyrolysisreactor, configured to cool pyrolyzed solids; and

(f) a high-carbon biogenic reagent recovery unit, disposed in operablecommunication with the cooler,

wherein the system is configured with at least one gas inlet forintroducing a substantially inert gas into the reactor, and at least onegas outlet for removing condensable vapors and non-condensable gasesfrom the reactor.

This system may include a deaerater disposed between the material feedsystem or the dryer (if present) and the preheater. The system may beconfigured with at least two gas inlets and at least two gas outlets, ifdesired.

In some embodiments, the pyrolysis reactor and/or the cooler isconfigured with gas inlet(s), and the dryer (if present) and/or thepreheater is configured with gas outlet(s), to generate substantiallycountercurrent flow of the gas phase relative to the solid phase.

The system further includes a process gas heater, in some embodiments,disposed in operable communication with the at least one gas outlet toremove condensable vapors and non-condensable gases. The process gasheater can be configured to introduce a separate fuel and an oxidantinto a combustion chamber, adapted for combustion of the fuel and atleast a portion of the condensable vapors.

The system may include a heat exchanger disposed between the process gasheater and the dryer, configured to utilize at least some of the heat ofthe combustion for the dryer. The system may include a heat exchangerdisposed between the process gas heater and a gas inlet for the BPU,configured to utilize at least some of the heat of the combustion forpreheating a substantially inert gas prior to introduction into thepyrolysis reactor.

Certain variations provide a biomass-pyrolysis continuous reactorcomprising a feedstock inlet, a plurality of spatially separatedreactors configured for separately controlling the temperature andmixing within each of the reactors, and a carbonaceous-solids outlet,wherein one of the reactors is configured with a first gas inlet forintroducing a substantially inert gas into the reactor, and wherein oneof the reactors is configured with a first gas outlet.

In some embodiments, the BPU includes at least two, three, or fourzones. Each of the zones may be disposed in communication withseparately adjustable indirect heating means, each independentlyselected from the group consisting of electrical heat transfer, steamheat transfer, hot-oil heat transfer, waste-heat transfer, andcombinations thereof.

The BPU may be configured for separately adjusting gas-phase compositionand gas-phase residence time of at least two zones. In some embodiments,the BPU is configured for separately adjusting gas-phase composition andgas-phase residence time of all zones present in the BPU.

In some embodiments, the BPU is configured with a second gas inletand/or a second gas outlet. In certain embodiments, the BPU isconfigured with a gas inlet in each zone and/or a gas outlet in eachzone. In some embodiments, the BPU is a countercurrent reactor.

The material feed system may comprise a feed mechanism selected from thegroup consisting of a screw, an auger, a drop chamber, and a drummaterial feed system. The carbonaceous-solids outlet may comprise anoutput mechanism selected from the group consisting of a screw, anauger, a drop chamber, and a drum material feed system. The BPU mayinclude a single auger disposed throughout each of the zones.

In some embodiments, each of the reactors is configured with flightsdisposed on internal walls, to provide agitation of solids. The flightsmay be separately adjustable in each of the zones. The BPU is an axiallyrotatable BPU, in some embodiments.

Still other variations of the invention provide a process for producinga high-carbon biogenic reagent, the process comprising:

(a) providing a carbon-containing feedstock comprising biomass;

(b) optionally drying the feedstock to remove at least a portion ofmoisture contained within the feedstock;

(c) optionally deaerating the feedstock to remove at least a portion ofinterstitial oxygen, if any, contained with the feedstock;

(d) in a pyrolysis zone, pyrolyzing the feedstock in the presence of asubstantially inert gas for at least about 10 minutes and with apyrolysis temperature selected from about 250° C. to about 700° C., togenerate hot pyrolyzed solids, condensable vapors, and non-condensablegases;

(e) separating at least a portion of the condensable vapors and at leasta portion of the non-condensable gases from the hot pyrolyzed solids;

(f) in a cooling zone, cooling the hot pyrolyzed solids, in the presenceof the substantially inert gas for at least about 5 minutes and with acooling temperature less than the pyrolysis temperature, to generatewarm pyrolyzed solids;

(g) optionally cooling the warm pyrolyzed solids in a separate cooler togenerate cool pyrolyzed solids;

(h) subsequently passing at least a portion of the condensable vaporsand/or at least a portion of the non-condensable gases from step (e)across the warm pyrolyzed solids and/or the cool pyrolyzed solids, toform enriched pyrolyzed solids with increased carbon content; and

(i) recovering a high-carbon biogenic reagent comprising at least aportion of the enriched pyrolyzed solids.

In some embodiments, step (h) includes passing at least a portion of thecondensable vapors from step (e), in vapor and/or condensed form, acrossthe warm pyrolyzed solids, to produce enriched pyrolyzed solids withincreased carbon and/or energy content. In these or other embodiments,step (h) includes passing at least a portion of the non-condensablegases from step (e) across the warm pyrolyzed solids, to produceenriched pyrolyzed solids with increased carbon and/or energy content.

In some embodiments, step (h) includes passing at least a portion of thecondensable vapors from step (e), in vapor and/or condensed form, acrossthe cool pyrolyzed solids, to produce enriched pyrolyzed solids withincreased carbon and/or energy content. In these or other embodiments,step (h) includes passing at least a portion of the non-condensablegases from step (e) across the cool pyrolyzed solids, to produceenriched pyrolyzed solids with increased carbon and/or energy content.

In certain embodiments, step (h) includes passing substantially all ofthe condensable vapors from step (e), in vapor and/or condensed form,across the cool pyrolyzed solids, to produce enriched pyrolyzed solidswith increased carbon and/or energy content. In these or otherembodiments, step (h) includes passing substantially all of thenon-condensable gases from step (e) across the cool pyrolyzed solids, toproduce enriched pyrolyzed solids with increased carbon content.

Energy may be recovered from the condensable vapors, the non-condensablegases, or both, for use in the process. Energy may be recovered throughheat exchange with these streams. Optionally, either or both of thecondensable vapors and non-condensable gases may be combusted, and theheat of combustion may be recovered for process use.

The process may further include introducing an intermediate feed streamconsisting of at least a portion of the condensable vapors and at leasta portion of the non-condensable gases, obtained from step (e), to aseparation unit configured to generate at least first and second outputstreams. The intermediate feed stream may include all of the condensablevapors and/or all of the non-condensable gases, in certain embodiments.A portion of the second output stream may be recycled to step (d) foruse as substantially inert gas in the pyrolysis unit, alone or incombination with another source of inert gas (e.g., N₂).

The first and second output streams may be separated based on relativevolatility, for example. In some embodiments, the first output streamcomprises the condensable vapors (e.g., terpenes, alcohols, acids,aldehydes, or ketones), and the second output stream comprises thenon-condensable gases (e.g., carbon monoxide, carbon dioxide, andmethane).

The first and second output streams may be separated based on relativepolarity. In these embodiments, the first output stream comprises polarcompounds (e.g., methanol, furfural, and acetic acid), and the secondoutput stream comprises non-polar compounds (e.g., carbon monoxide,carbon dioxide, methane, terpenes, and terpene derivatives).

In some embodiments, step (h) increases the total carbon content, fixedcarbon content, and/or energy content of the high-carbon biogenicreagent, relative to an otherwise-identical process without step (h). Insome embodiments, step (h) increases the fixed carbon content of thehigh-carbon biogenic reagent, relative to an otherwise-identical processwithout step (h).

This invention also provides a continuous or batch process forincreasing carbon and/or energy content of any carbon-containingmaterial. In some variations, a process for producing a high-carbonbiogenic reagent comprises:

(a) providing a solid stream comprising a starting carbon-containingmaterial;

(b) providing a gas stream comprising condensable carbon-containingvapors, non-condensable carbon-containing gases, or a mixture ofcondensable carbon-containing vapors and non-condensablecarbon-containing gases; and

(c) passing the gas stream across the solid stream under suitableconditions to form a carbon-containing product with increased carbonand/or energy content relative to the carbon-containing material.

In some embodiments, the starting carbon-containing material ispyrolyzed biomass or torrefied biomass. The gas stream may be obtainedduring an integrated process that provides the carbon-containingmaterial. Or, the gas stream may be obtained from separate processing ofthe carbon-containing material. The gas stream, or a portion thereof,may be obtained from an external source. Mixtures of gas streams, aswell as mixtures of carbon-containing materials, from a variety ofsources, are possible.

In some embodiments, the process further comprises recycling or reusingthe gas stream for repeating the process to further increase carbonand/or energy content of the carbon-containing product. In someembodiments, the process further comprises recycling or reusing the gasstream for carrying out the process to increase carbon and/or energycontent of another feedstock different from the carbon-containingmaterial.

This process may include introducing the gas stream to a separation unitconfigured to generate at least first and second output streams, whereinthe gas stream comprises a mixture of condensable carbon-containingvapors and non-condensable carbon-containing gases. The first and secondoutput streams may be separated based on relative volatility or relativepolarity, for example.

In some embodiments, the carbon-containing product has higher totalcarbon content and/or fixed carbon content and/or volatile carboncontent than the carbon-containing material. In some embodiments, thecarbon-containing product has higher energy content than thecarbon-containing material.

A high-carbon biogenic reagent production system is also provided, thesystem comprising:

(a) a material feed system configured to introduce a carbon-containingfeedstock;

(b) an optional dryer, disposed in operable communication with thematerial feed system, configured to remove moisture contained within acarbon-containing feedstock;

(c) a BPU, disposed in operable communication with the material feedsystem or the dryer (if present), wherein the BPU contains at least onepyrolysis zone disposed in operable communication with a spatiallyseparated cooling zone, and wherein the BPU is configured with an outletto remove condensable vapors and non-condensable gases from solids;

(d) an optional cooler, disposed in operable communication with the BPU;

(e) a material-enrichment unit, disposed in operable communication withthe BPU or the cooler (if present), configured to pass the condensablevapors and/or the non-condensable gases across the solids, to formenriched solids with increased carbon content; and

(f) a carbon recovery unit, disposed in operable communication with thematerial-enrichment unit.

In some embodiments, the system further comprises a preheating zone,disposed in operable communication with the pyrolysis zone. Each of thepyrolysis zone, the cooling zone, and the preheating zone (if present)may be located within a single unit, or in separate units. The dryer, ifpresent, may be configured as a drying zone within the BPU.

The cooling zone may be configured with a gas inlet, and the pyrolysiszone may be configured with a gas outlet, to generate substantiallycountercurrent flow of the gas phase relative to the solid phase. Thecooling zone may be configured with a gas inlet, and the preheating zoneand/or drying zone may be configured with a gas outlet, to generatesubstantially countercurrent flow of the gas phase relative to the solidphase.

In certain embodiments, the material-enrichment unit comprises:

(i) a housing with an upper portion and a lower portion;

(ii) an inlet at a bottom of the lower portion of the housing configuredto carry the condensable vapors and non-condensable gases;

(iii) an outlet at a top of the upper portion of the housing configuredto carry a concentrated gas stream derived from the condensable vaporsand non-condensable gases;

(iv) a path defined between the upper portion and the lower portion ofthe housing; and

(v) a transport system following the path, the transport systemconfigured to transport the solids, wherein the housing is shaped suchthat the solids adsorb at least some of the condensable vapors and/or atleast some of the non-condensable gases.

This invention also provides various products and compositions. In somevariations, a high-carbon biogenic reagent is produced by a processcomprising the steps of:

(a) providing a carbon-containing feedstock comprising biomass;

(b) optionally drying the feedstock to remove at least a portion ofmoisture contained within the feedstock;

(c) optionally deaerating the feedstock to remove at least a portion ofinterstitial oxygen, if any, contained with the feedstock;

(d) in a pyrolysis zone, pyrolyzing the feedstock in the presence of asubstantially inert gas for at least about 10 minutes and with apyrolysis temperature selected from about 250° C. to about 700° C., togenerate hot pyrolyzed solids, condensable vapors, and non-condensablegases;

(e) separating at least a portion of the condensable vapors and at leasta portion of the non-condensable gases from the hot pyrolyzed solids;

(f) in a cooling zone, cooling the hot pyrolyzed solids, in the presenceof the substantially inert gas for at least about 5 minutes and with acooling-zone temperature less than the pyrolysis temperature, togenerate warm pyrolyzed solids;

(g) in an optional cooler that is separate from the cooling zone,cooling the warm pyrolyzed solids to generate cool pyrolyzed solids; and

(h) recovering a high-carbon biogenic reagent comprising at least aportion of the warm or cool pyrolyzed solids.

The high-carbon biogenic reagent may further comprise at least oneprocess additive incorporated during the process. Alternatively, oradditionally, the high-carbon biogenic reagent may further include atleast one product additive introduced to the reagent following theprocess.

In some embodiments, the process additive and/or the product additive isselected to increase the carbon content and/or the energy content of thehigh-carbon biogenic reagent. In some embodiments, the process additiveand/or the product additive is selected to maintain the structuralintegrity or mechanical strength of the high-carbon biogenic reagentrelative to said feedstock. Additives may be useful to help maintainstructural form prior to use of the biogenic reagent.

In some embodiments, the high-carbon biogenic reagent comprises at least55 wt. %, at least 60 wt. %, at least 65 wt. %, at least 70 wt %, atleast 80 wt %, at least 90 wt %, or at least 95 wt % total carbon on adry basis. The total carbon includes fixed carbon and carbon fromvolatile matter. In some embodiments, the carbon from volatile matter isat least 5%, at least 20%, or at least 40% of the total carbon.

In some embodiments, the high-carbon biogenic reagent comprises about 10wt % or less hydrogen, such as about 5 wt % or less hydrogen on a drybasis. In some embodiments, the reagent comprises about 20 wt % or lessoxygen, such as between about 1 wt % and about 10 wt % oxygen on a drybasis. In some embodiments, the high-carbon biogenic reagent comprisesabout 1 wt % or less nitrogen, such as about 0.5 wt % or less nitrogenon a dry basis. In some embodiments, the reagent comprising about 0.5 wt% or less phosphorus, such as about 0.2 wt % or less phosphorus on a drybasis. In some embodiments, the high-carbon biogenic reagent comprisingabout 0.2 wt % or less sulfur, such as about 0.1 wt % or less sulfur ona dry basis.

In some embodiments, the high-carbon biogenic reagent comprises about 10wt % or less non-combustible matter (e.g., ash) on a dry basis. Incertain embodiments, the high-carbon biogenic reagent comprises about 5wt % or less, or about 1 wt % or less, non-combustible matter on a drybasis. The high-carbon biogenic reagent may further contain moisture atvarying levels.

The high-carbon biogenic reagent may have an energy content of at least11,000 Btu/lb, at least 12,000 Btu/lb, at least 13,000 Btu/lb, at least14,000 Btu/lb, or at least 14,500 Btu/lb on a dry basis. In exemplaryembodiments, the high-carbon biogenic reagent has an energy content ofat least 14,700 Btu/lb and a fixed carbon content of at least 95 wt % ona dry basis.

In some embodiments, a high-carbon biogenic reagent comprises, on a drybasis:

55 wt % or more total carbon;

5 wt % or less hydrogen;

1 wt % or less nitrogen;

0.5 wt % or less phosphorus;

0.2 wt % or less sulfur; and

an additive selected from a metal, a metal oxide, a metal hydroxide, ametal halide, or a combination thereof.

The additive may be selected from the group consisting of magnesium,manganese, aluminum, nickel, chromium, silicon, boron, cerium,molybdenum, phosphorus, tungsten, vanadium, iron halide, iron chloride,iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorite,fluorospar, bentonite, calcium oxide, lime, and combinations thereof.

In some embodiments, a high-carbon biogenic reagent comprises, on a drybasis:

55 wt % or more total carbon;

5 wt % or less hydrogen;

1 wt % or less nitrogen;

0.5 wt % or less phosphorus;

0.2 wt % or less sulfur; and

an additive selected from an acid, a base, or a salt thereof.

The additive may be selected from the group consisting of sodiumhydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide,hydrogen chloride, sodium silicate, potassium permanganate, andcombinations thereof.

In certain embodiments, a high-carbon biogenic reagent comprises, on adry basis:

55 wt % or more total carbon;

5 wt % or less hydrogen;

1 wt % or less nitrogen;

0.5 wt % or less phosphorus;

0.2 wt % or less sulfur;

a first additive selected from a metal, a metal oxide, a metalhydroxide, a metal halide, or a combination thereof; and

a second additive selected from an acid, a base, or a salt thereof,

wherein the first additive is different from the second additive.

The first additive may be selected from the group consisting ofmagnesium, manganese, aluminum, nickel, chromium, silicon, boron,cerium, molybdenum, phosphorus, tungsten, vanadium, iron halide, ironchloride, iron bromide, magnesium oxide, dolomite, dolomitic lime,fluorite, fluorospar, bentonite, calcium oxide, lime, and combinationsthereof, and the second additive may be independently selected from thegroup consisting of sodium hydroxide, potassium hydroxide, magnesiumoxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassiumpermanganate, and combinations thereof.

The high-carbon biogenic reagent may comprise about 55 wt. %, 60 wt. %,65 wt. %, 70 wt %, 75 wt %, 80 wt %, 85 wt %, 90 wt %, 95 wt %, or moretotal carbon on a dry basis (total carbon includes fixed carbon andcarbon associated with volatile matter).

In some embodiments, the reagent comprises about 8 wt % or lessnon-combustible matter on a dry basis, such as about 4 wt % or lessnon-combustible matter on a dry basis.

A high-carbon biogenic reagent may consisting essentially of, on a drybasis, carbon, hydrogen, oxygen, nitrogen, phosphorus, sulfur,non-combustible matter, and an additive selected from the groupconsisting of magnesium, manganese, aluminum, nickel, chromium, silicon,boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron halide,iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime,fluorite, fluorospar, bentonite, calcium oxide, lime, and combinationsthereof. Moisture may be present or absent.

A high-carbon biogenic reagent may consisting essentially of, on a drybasis, carbon, hydrogen, nitrogen, phosphorus, sulfur, non-combustiblematter, and an additive selected from the group consisting of sodiumhydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide,hydrogen chloride, sodium silicate, potassium permanganate, andcombinations thereof. Moisture may be present or absent.

The high-carbon biogenic reagent may have an energy content of at least11,000 Btu/lb, at least 12,000 Btu/lb, at least 13,000 Btu/lb, at least14,000 Btu/lb, or at least 14,500 Btu/lb on a dry basis.

The high-carbon biogenic reagent may be a fine powder, or may be in theform of structural objects. Structural objects may be derived frompressing, binding, pelletizing, or agglomerating particles. In someembodiments, the structural objects have a structure and/or strengththat substantially derive from the feedstock source of the carbon. Incertain embodiments, the structural objects have substantially the samestructural form as the feedstock source of the carbon.

In some embodiments of the high-carbon biogenic reagent, the majority ofthe carbon is classified as renewable carbon. Substantially all of thecarbon contained within certain high-carbon biogenic reagents may beclassified as renewable carbon.

The present invention also provides a wide variety of carbonaceousproducts comprising high-carbon biogenic reagents. Such carbonaceousproducts include, but are not limited to, blast furnace additionproducts, taconite pellet process addition products, taconite pellets,coal replacement products, coking carbon products, carbon breezeproducts, fluidized-bed products, furnace addition products, injectablecarbon products, ladle addition carbon products, met coke products,pulverized carbon products, stoker carbon products, carbon electrodes,and activated carbon products. These and other embodiments are describedin further detail below.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 depicts a multi-reactor embodiment of a system of the invention.

FIG. 2 depicts a single reactor, multi-zone embodiment of a system ofthe invention

FIG. 3 depicts one embodiment of a zero-oxygen continuous feed mechanismsuitable for use in connection with the present invention.

FIG. 4 depicts another embodiment of a single reactor, multi-zonebiomass processing unit suitable for use in connection with the presentinvention.

FIG. 5 depicts one embodiment of a carbon recovery unit suitable for usein connection with the present invention.

FIG. 6 depicts an embodiment of one embodiment of a single-reactorbiomass processing unit of the present invention with an optional dryer.

FIG. 7 depicts a pyrolysis reactor system embodiment of the inventionwith an optional dryer and a gas inlet.

FIG. 8 depicts an embodiment of a single-reactor biomass processing unitof the invention with a gas inlet and an optional cooler.

FIG. 9 depicts a single-reactor biomass processing unit systemembodiment of the invention with an optional dryer and de-aerator, andan inert gas inlet.

FIG. 10 depicts a multiple-reactor system embodiment of the inventionwith an optional dryer and de-aerator, and an inert gas inlet.

FIG. 11 depicts a multiple-reactor system embodiment of the inventionwith an optional dryer and cooler, and a material enrichment unit.

FIG. 12 depicts a multiple-reactor system embodiment of the inventionwith an optional dryer, de-aerator, a cooler, and an inert gas inlet.

FIG. 13 depicts a multiple-reactor system embodiment of the inventionwith an optional dryer and de-aerator, an inert gas inlet, and a cooler.

FIG. 14 depicts a graph illustrating the effect of retention time onfixed carbon content of a biogenic reagent produced according to oneembodiment of the present disclosure.

FIG. 15 depicts a graph illustrating the effect of pyrolysis temperatureon fixed carbon content of a biogenic reagent produced according to oneembodiment of the present disclosure.

FIG. 16 depicts a graph illustrating the effect of biomass particle sizeon fixed carbon content of a biogenic reagent produced according to oneembodiment of the present disclosure.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

This description will enable one skilled in the art to make and use theinvention, and it describes several embodiments, adaptations,variations, alternatives, and uses of the invention. These and otherembodiments, features, and advantages of the present invention willbecome more apparent to those skilled in the art when taken withreference to the following detailed description of the invention inconjunction with the accompanying drawings.

As used in this specification and the appended claims, the singularforms “a,” “an,” and “the” include plural referents unless the contextclearly indicates otherwise. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as is commonlyunderstood by one of ordinary skill in the art to which this inventionbelongs.

Unless otherwise indicated, all numbers expressing reaction conditions,stoichiometries, concentrations of components, and so forth used in thespecification and claims are to be understood as being modified in allinstances by the term “about.” Accordingly, unless indicated to thecontrary, the numerical parameters set forth in the followingspecification and attached claims are approximations that may varydepending at least upon a specific analytical technique.

The term “comprising,” which is synonymous with “including,”“containing,” or “characterized by” is inclusive or open-ended and doesnot exclude additional, unrecited elements or method steps. “Comprising”is a term of art used in claim language which means that the named claimelements are essential, but other claim elements may be added and stillform a construct within the scope of the claim.

As used herein, the phase “consisting of” excludes any element, step, oringredient not specified in the claim. When the phrase “consists of” (orvariations thereof) appears in a clause of the body of a claim, ratherthan immediately following the preamble, it limits only the element setforth in that clause; other elements are not excluded from the claim asa whole. As used herein, the phase “consisting essentially of” limitsthe scope of a claim to the specified elements or method steps, plusthose that do not materially affect the basis and novelcharacteristic(s) of the claimed subject matter.

With respect to the terms “comprising,” “consisting of,” and “consistingessentially of,” where one of these three terms is used herein, thepresently disclosed and claimed subject matter may include the use ofeither of the other two terms. Thus in some embodiments not otherwiseexplicitly recited, any instance of “comprising” may be replaced by“consisting of” or, alternatively, by “consisting essentially of.”

For present purposes, “biogenic” is intended to mean a material (whethera feedstock, product, or intermediate) that contains an element, such ascarbon, that is renewable on time scales of months, years, or decades.Non-biogenic materials may be non-renewable, or may be renewable on timescales of centuries, thousands of years, millions of years, or evenlonger geologic time scales. Note that a biogenic material may include amixture of biogenic and non-biogenic sources.

For present purposes, “reagent” is intended to mean a material in itsbroadest sense; a reagent may be a fuel, a chemical, a material, acompound, an additive, a blend component, a solvent, and so on. Areagent is not necessarily a chemical reagent that causes orparticipates in a chemical reaction. A reagent may or may not be achemical reactant; it may or may not be consumed in a reaction. Areagent may be a chemical catalyst for a particular reaction. A reagentmay cause or participate in adjusting a mechanical, physical, orhydrodynamic property of a material to which the reagent may be added.For example, a reagent may be introduced to a metal to impart certainstrength properties to the metal. A reagent may be a substance ofsufficient purity (which, in the current context, is typically carbonpurity) for use in chemical analysis or physical testing.

By “high-carbon” as used in this application to describe biogenicreagents, it is meant simply that the biogenic reagent has a relativelyhigh carbon content as compared to the initial feedstock utilized toproduce the high-carbon biogenic reagent. Typically, a high-carbonbiogenic reagent will contain at least about half its weight as carbon.More typically, a high-carbon biogenic reagent will contain at least 55wt %, 60 wt %, 65 wt %, 70 wt %, 80 wt %, 90 wt % or higher carbon.

Notwithstanding the foregoing, the term “high-carbon biogenic reagent”is used herein for practical purposes to consistently describe materialsthat may be produced by processes and systems of the invention, invarious embodiments. Limitations as to carbon content, or any otherconcentrations, shall not be imputed from the term itself but ratheronly by reference to particular embodiments and equivalents thereof. Forexample it will be appreciated that a starting material having very lowcarbon content, subjected to the disclosed processes, may produce ahigh-carbon biogenic reagent that is highly enriched in carbon relativeto the starting material (high yield of carbon), but neverthelessrelatively low in carbon (low purity of carbon), including less than 50wt % carbon.

“Pyrolysis” and “pyrolyze” generally refer to thermal decomposition of acarbonaceous material. In pyrolysis, less oxygen is present than isrequired for complete combustion of the material, such as less than 10%,5%, 1%, 0.5%, 0.1%, or 0.01% of the oxygen that is required for completecombustion. In some embodiments, pyrolysis is performed in the absenceof oxygen.

Exemplary changes that may occur during pyrolysis include any of thefollowing: (i) heat transfer from a heat source increases thetemperature inside the feedstock; (ii) the initiation of primarypyrolysis reactions at this higher temperature releases volatiles andforms a char; (iii) the flow of hot volatiles toward cooler solidsresults in heat transfer between hot volatiles and cooler unpyrolyzedfeedstock; (iv) condensation of some of the volatiles in the coolerparts of the feedstock, followed by secondary reactions, can producetar; (v) autocatalytic secondary pyrolysis reactions proceed whileprimary pyrolytic reactions simultaneously occur in competition; and(vi) further thermal decomposition, reforming, water-gas shiftreactions, free-radical recombination, and/or dehydrations can alsooccur, which are a function of the residence time, temperature, andpressure profile.

Pyrolysis can at least partially dehydrate the feedstock. In variousembodiments, pyrolysis removes greater than about 50%, 75%, 90%, 95%,99%, or more of the water from the feedstock.

As discussed above, some variations of the invention are premised, atleast in part, on the discovery that multiple reactors or multiple zoneswithin a single reactor can be designed and operated in a way thatoptimizes carbon yield and product quality from pyrolysis, whilemaintaining flexibility and adjustability for feedstock variations andproduct requirements.

Generally speaking, the temperatures and residence times are selected toachieve relatively slow pyrolysis chemistry. The benefit is potentiallythe substantial preservation of cell walls contained in the biomassstructure, which means the final product can retain some, most, or allof the shape and strength of the starting biomass. In order to maximizethis potential benefit, an apparatus that does not mechanically destroythe cell walls or otherwise convert the biomass particles into smallfines can be utilized. Various reactor configurations are discussedfollowing the process description below.

Additionally, if the feedstock is a milled or sized feedstock, such aswood chips or pellets, it may be desirable for the feedstock to becarefully milled or sized. Careful initial treatment will tend topreserve the strength and cell-wall integrity that is present in thenative feedstock source (e.g., trees). This can also be important whenthe final product should retain some, most, or all of the shape andstrength of the starting biomass.

In various embodiments, measures are taken to preserve the vascularstructure of woody feedstock to create greater strength in biogenicreagents. For example, and without limitation, in various embodimentsthe feedstock is prepared by drying feedstock over an extended period oftime, for example over a period of time of no less than 1 hour, no lessthan 2 hours, no less than 3 hours, no less than 4 hours, no less than 5hours, no less than 6 hours, no less than 7 hours, no less than 8 hours,no less than 9 hours, no less than 10 hours, no less than 11 hours, noless than 12 hours, no less than 13 hours, no less than 14 hours, noless than 15 hours, no less than 16 hours, no less than 17 hours, noless than 18 hours, no less than 19 hours, no less than 20 hours, noless than 21 hours, no less than 22 hours, no less than 23 hours, or noless than 24 hours, to allow water and gases to exit the biomass withoutdestroying the vascular structure of the feedstock. In variousembodiments, use of a slow progressive heat rate during pyrolysis (forexample in contrast to flash pyrolysis) over minutes or hours is used toallow water and gases to exit the biomass without destroying thevascular structure of the feedstock. For example and without limitation,a rate of temperature increase during the pyrolysis step may range fromabout 1° C. per minute to about 40° C. per minute, for example about 1°C. per minute, about 2° C. per minute, about 4° C. per minute, about 5°C. per minute, about 10° C. per minute, about 15° C. per minute, about20° C. per minute, about 25° C. per minute, about 30° C. per minute,about 35° C. per minute, or about 40° C. per minute. In someembodiments, the temperature increase occurs in a pre-heat zone toproduce a preheated feedstock. In some embodiments, the temperatureincrease occurs predominantly or entirely in a pre-heat zone to producea preheated feedstock. In some embodiments, the temperature of apreheated feedstock is increased in a pre-pyrolysis zone. In someembodiments, the temperature increase occurs at least in part in acarbonization zone or a pyrolysis zone. In some embodiments, thetemperature increase occurs predominantly or entirely in a carbonizationzone or a pyrolysis zone. In some embodiments, a preheat zone,pre-pyrolysis zone, carbonization zone or pyrolysis zone is configuredto increase the temperature during pyrolysis from an initial, lowtemperature to a final, higher temperature over time. In someembodiments, the temperature increase is linear or substantially linearover time. In some embodiments, the rate of temperature increaseincreases or decreases over time such that the temperature duringpreheating, pre-pyrolysis and/or carbonization or pyrolysis is at leastpartially nonlinear, for example logarithmic or substantiallylogarithmic for at least a portion of the preheat, pre-pyrolysis and/orcarbonization or pyrolysis step. In various embodiments, an additive isused prior to drying or pyrolysis to reduce gas formation that coulddamage the vascular structure of the feedstock during pyrolysis. Invarious embodiments, prior to pyrolysis, dried feedstock is sized usinga saw or other cutting device designed to be less destructive to thevascular structure of wood than other sizing approaches such as chippingor shearing wet wood that fractures wood and decreases its strength. Insuch embodiments, a biogenic reagent has a greater strength index (e.g.,CSR value) than a comparable biogenic reagent not prepared in such amanner.

In various embodiments, the feedstock is prepared by milling biomass toform a plurality of biomass pieces that are substantially uniform sizeand substantially uniform shape. For example and without limitation,biomass can be processed to produce sawdust of approximately uniformgrain size (e.g., mesh size). Alternatively, biomass can be processed toproduce chips having substantially uniform dimensions (e.g.,approximately 1 inch by approximately ½-inch by approximately ⅛-inchpieces). In other embodiments, feedstock can be prepared by millingbiomass to form lengths of material with substantially uniform width anddepth dimensions or diameters (e.g., wood bars, boards or dowels). Inrelated embodiments, the lengths of material having substantiallyuniform width and depth or diameter can be further milled to producefeedstock pieces of substantially uniform lengths, resulting in afeedstock material having substantially uniform size and shape. Forexample, wood dowels having a uniform diameter (e.g., about 1⅛ inches)can be cut into pieces of substantially uniform length (e.g., about 1.5inches). The resulting feedstock pieces have a substantially uniformshape (cylinders) and a substantially uniform size (about 1⅛ inchdiameter by about 1.5 inch lengths). In some embodiments, a biogenicreagent prepared from a feedstock consisting of pieces of substantiallyuniform shape and size is produced in greater mass yield than acomparable biogenic reagent prepared from feedstock pieces ofsubstantially non-uniform shape and/or size.

Referring now generally to FIGS. 1 to 13, block flow diagrams of aseveral exemplary multi reactor embodiments of the present disclosureare illustrated. Each figure is discussed in turn below. It should beappreciated FIGS. 1 to 13 represent some example embodiments but not allcontemplated embodiments of the present disclosure. As discussed below,various additional non-illustrated embodiments and combinations of theseveral components and features discussed herein are also contemplated.As will be understood in the discussion below, any of the plurality ofreactors discussed herein can be independent reactors, or alternativelywithin a single reactor BPU can include a plurality of zones, or acombination thereof. It should be appreciated that, although the figureseach illustrate a different alternative embodiment, all other discussionin this disclosure can apply to each of the illustrated andnon-illustrated embodiments.

Referring now generally to FIG. 1, a block flow diagram of a multireactor embodiment of the present disclosure is illustrated. Thisembodiment can utilize two to a plurality of different reactors. Threereactors are shown in the illustrative embodiment, however, anydifferent number of reactors could be employed. In one embodiment, eachreactor is connected to at least one other reactor via a materialtransport unit 304 (shown in FIG. 3). In one embodiment, the materialtransport unit 304 controls atmosphere and temperature conditions.

In the illustrated embodiment, the raw material 109, such as biomass, isoptionally dried and sized outside the system and introduced into thefirst reactor 100 in a low-oxygen atmosphere, optionally through the useof a material feed system 108. As discussed in further detail below andas illustrated in FIG. 3, the material feed system 108 reduces theoxygen level in the ambient air in the system to not more than about 3%.The raw material 109 enters the first reactor 112 via the enclosedmaterial transport unit 304 after the oxygen levels have been decreasedin the first reactor. In one embodiment, the raw material transport unitwill include an encapsulated jacket or sleeve through which steam andoff-gases from the reactor are sent and used to pre-heat the biomasseither directly or sent to a process gas heater and or heat exchangerand then sent and used to pre-heat or pyrolize the biomass.

In the illustrated embodiment, the raw material 109 first travels fromthe material feed system 108 on the material transport unit 304 into thefirst reactor of the BPU 112.

As discussed in more detail below, in one embodiment, the first reactor112 is configured to be connected to any other reactor in the system torecover waste heat 132 and conserve energy through a suitable waste heatrecovery system. In one embodiment, the waste heat given off in thefirst reactor 112 is used to operate a steaming bin or anotherappropriate heating mechanism configured to dry raw materials 109 insideor outside of the system. In various embodiments, other byproducts ofthe waste heat, such as a substantially heated inert gas or the like,can be used elsewhere in the system to further enrich the material atany point along the process.

In the illustrated embodiment, the biomass 109 enters the first reactor112, wherein the temperature is raised from the range of about ambienttemperature to about 150° C. to a temperature of about 100° C. to about200° C. In one embodiment, the temperature does not exceed 200° C. inthe first reactor 112. As discussed in greater detail below, the firstreactor 112 can include an output mechanism to capture and exhaustoff-gases 120 from the biomass 123 while it is being heated. In oneembodiment, the off-gases 120 are extracted for optional later use. Invarious embodiments, the heating source used for the various zones inthe BPU 102 is electrical or gas. In one embodiment, the heating sourceused for the various reactors of the BPU 102 is waste gas from otherreactors of the unit 102 or from external sources. In variousembodiments, the heat is indirect.

Following preheating in the first reactor 112, the material transportunit 304 passes the preheated material 123 into the optional secondreactor 114. In one embodiment reactor 114 is the same as reactor 112.In one embodiment where reactor 114 is different than reactor 112, thematerial transport unit 304 penetrates the second reactor 114 through ahigh-temperature vapor seal system (e.g. an airlock), which allows thematerial transport unit 304 to penetrate the second reactor whilepreventing gas from escaping. In one embodiment, the interior of thesecond reactor 114 is heated to a temperature of about 100° C. to about600° C. or about 200° C. to about 600° C. In another embodiment, thesecond reactor 114 includes an output port similar to the first reactor102 to capture and exhaust the gases 122 given off of the preheatedmaterial 123 while it is being carbonized. In one embodiment, the gases122 are extracted for optional later use. In one illustrativeembodiment, the off-gases 120 from the first reactor 112 and theoff-gases 122 from the second reactor 114 are combined into one gasstream 124. Once carbonized, the carbonized biomass 125 exits the secondreactor 114 and enters the third reactor 116 for cooling. Again, thethird reactor can be the same reactor as 112 or 114 or different.

In one embodiment, when the biogenic reagent 125 enters the thirdreactor 116, the carbonized biomass 125 is allowed to cool (actively orpassively) to a specified temperature range to form carbonized biomass126, as discussed above. In one embodiment, temperature of thecarbonized biomass 125 is reduced in the third reactor undersubstantially inert atmospheric conditions. In another embodiment, thethird reactor cools the carbonized biomass 125 with an additional watercooling mechanism. It should be appreciated that the carbonized biomass126 is allowed to cool in the third reactor 116 to the point where itwill not spontaneously combust if exposed to oxygenated air. In one suchembodiment, the third reactor 116 reduces temperature of the carbonizedbiomass to below 200° C. In one embodiment, the third reactor includes amixer (not shown) to agitate and uniformly cool the carbonized biomass.It should be appreciated that cooling may occur either directly orindirectly with water or other liquids; cooling may also occur eitherdirectly or indirectly with air or other cooled gases, or anycombination of the above.

It should be appreciated that in several embodiments (not shown) one ormore additional coolers or cooling mechanisms are employed to furtherreduce the temperature of the carbonized biomass. In various suchembodiments, the cooler is separate from the other reactors 112, 114,116, along the material transport system. In some embodiments, thecooler follows the reactors. In some embodiments, the cooler can be thesame as the reactors 112, 114, 116. In other embodiments, the cooler is,for example, a screw, auger, conveyor (specifically a belt conveyor inone embodiment), drum, screen, pan, counterflow bed, vertical tower,jacketed paddle, cooled screw or combination thereof that cools eitherdirectly or indirectly with water or other liquids, or directly orindirectly with other gases, or combination of the above. In variousembodiments, coolers could include water spray, cooled inert gasstreams, liquid nitrogen, or ambient air if below ignition temperature.It should be appreciated that heat can be recovered from this step bycapturing the flash steam generated by the water spray, or thesuperheated steam generated when saturated steam is introduced andheated by the carbonized biomass.

As illustrated in FIGS. 1 and 5, the gas-phase separator unit 200includes at least one input and a plurality of outputs. The at least oneinput is connected to the exhaust ports on the first reactor 112 and thesecond reactor 114 of the BPU 102. One of the outputs is connected tothe carbon recovery unit 104, and another one of the outputs isconnected to collection equipment or further processing equipment suchas an acid hydrogenation unit 106 or distillation column. In variousembodiments, the gas-phase separator processes the off-gases 120, 122from the first reactor 112 and the second reactor 114 to produce acondensate 128 and an enrichment gas 204. In various embodiments,condensables may be used for either energy recovery (134) (for examplein the dryer, reactor or process gas heater), or for other carbonenrichment. In various embodiments, non-condensables (for example CO)may be used for energy recovery (134) (for example in a dryer, reactoror process gas heater), as an inert gas in the process (for example inthe deaeration unit, reactor, BPU or cooler discussed in more detailbelow) or for carbon enrichment.

In various embodiments, the condensate 128 includes polar compounds,such as acetic acid, methanol and furfural. In another embodiment, theenrichment gas 204 produced by the gas-phase separator 200 includes atleast non-polar gases, for example carbon monoxide, terpenes, methane,carbon dioxide, etc. In one embodiment, the gas-phase separatorcomprises a fractionation column. In one embodiment, acetic acid is sentvia a line 128 to an optional acid hydrogenation unit. In anotherembodiment, methanol and/or furfural are sent via optional additionalline(s) 136 to a distillation/processing unit 138

In various embodiments, as discussed in more detail below, the carbonrecovery unit itself has the facility to enrich the material. In variousother embodiments, the material is enriched in a material enrichmentunit separate from the carbon recovery unit. It should be appreciatedthat, in some such embodiments, the carbon recovery unit is a vessel forstoring the carbonized material, and the separate material enrichmentunit is the unit in which gases are introduced to enrich the material.

In the illustrated embodiment, the carbon recovery unit 500 alsoenriches the carbonized biomass 126. The carbonized biomass 126 exitsthe third reactor along the material transport unit 304 and enters thecarbon recovery unit 500. In various embodiments, as illustrated in moredetail in FIG. 5 and discussed above, the carbon recovery unit 500 alsoincludes an input 524 connected to the gas-phase separator 200. In oneembodiment, the enrichment gas 204 is directed into the carbon recoveryunit to be combined with the biogenic reagent 126 to create a highcarbon biogenic reagent 136. In another embodiment, a carbon-enrichedgas from an external source can also be directed to the carbon recoveryunit to be combined with the carbonized biomass 126 to add additionalcarbon to the ultimate high carbon biogenic reagent produced. In variousembodiments, the carbonized biomass 126 is temperature-reducedcarbonized biomass. Illustratively, the system 100 can be co-locatednear a timber processing facility and carbon-enriched gas from thetimber processing facility can be used as gas from an external source.

Referring now generally to FIG. 2, a block flow diagram of a singlereactor, multi-zone embodiment of the present disclosure is illustrated.In the illustrated embodiment, the raw material 209, such as biomass, isintroduced into the reactor 200 in a low-oxygen atmosphere, optionallythrough the use of a material feed system 108 already described. Asdiscussed in further detail below, the material feed system 108 reducesthe oxygen level in the ambient air in the system to not more than about3%. The raw material 209 enters the BPU 202 in an enclosed materialtransport unit 304 after the oxygen levels have been decreased. In oneembodiment, the material transport unit will include an encapsulatedjacket or sleeve through which steam and off-gases from the reactor 200are sent and used to pre-heat the biomass.

In the illustrated embodiment, the raw material first travels from thematerial feed system 108 on the material transport unit 304 through anoptional drying zone 210 of the BPU 202. In one embodiment, the optionaldrying zone 210 heats the raw material to remove water and othermoisture prior to being passed along to the preheat zone 212. In oneembodiment, the interior of the optional drying zone 210 is heated to atemperature of about ambient temperature to about 150° C. Water 238 orother moisture removed from the raw material 209 can be exhausted, forexample, from the optional drying zone 210. In another embodiment, theoptional drying zone is adapted to allow vapors and steam to beextracted. In another embodiment, vapors and steam from the optionaldrying zone are extracted for optional later use. As discussed below,vapors or steam extracted from the optional drying zone can be used in asuitable waste heat recovery system with the material feed system. Inone embodiment, the vapors and steam used in the material feed systempre-heat the raw materials while oxygen levels are being purged in thematerial feed system. In another embodiment, biomass is dried outside ofthe reactor and the reactor does not comprise a drying zone.

As discussed in more detail below, in one embodiment, the optionaldrying zone 210 is configured to be connected to the cooling zone 216 torecover waste heat 232 and conserve energy through a suitable waste heatrecovery system. In one embodiment, the waste heat given off in thecooling zone 216 is used to operate a heating mechanism configured todry raw materials 209 in the optional drying zone 210. After being driedfor a desired period of time, the dried biomass 221 exits the optionaldrying zone 210 and enters preheat zone 212.

In the illustrated embodiment, the dried biomass 221 enters the first(preheat) zone 212, wherein the temperature is raised from the range ofabout ambient temperature to about 150° C. to a temperature range ofabout 100° C. to about 200° C. In one embodiment, the temperature doesnot exceed 200° C. in the first/preheat zone 212. It should beappreciated that if the preheat zone 212 is too hot or not hot enough,the dried biomass 221 may process incorrectly prior to entering thesecond zone 214. As discussed in greater detail below, the preheat zone212 can includes an output mechanism to capture and exhaust off-gases220 from the dried biomass 221 while it is being preheated. In anotherembodiment, the off-gases 220 are extracted for optional later use. Invarious embodiments, the heating source used for the various zones inthe BPU 202 is electric or gas. In one embodiment, the heating sourceused for the various zones of the BPU 202 is waste gas from other zonesof the unit 202 or from external sources. In various embodiments, theheat is indirect.

Following the preheat zone 212, the material transport unit 304 passesthe preheated material 223 into the second (pyrolysis) zone 214. In oneembodiment, the material transport unit 304 penetrates thesecond/pyrolysis zone through a high-temperature vapor seal system (suchas an airlock, not shown), which allows the material transport unit 304to penetrate the high-temperature pyrolysis zone while preventing (orminimizing) gas from escaping. In one embodiment, the interior of thepyrolysis zone 214 is heated to a temperature of about 100° C. to about600° C. or about 200° C. to about 500° C. In another embodiment, thepyrolysis zone 214 includes an output port similar to the preheat zone212 to capture and exhaust the gases 222 given off of the preheatedbiomass 223 while it is being carbonized. In one embodiment, the gases222 are extracted for optional later use. In one illustrativeembodiment, the off-gases 220 from the preheat zone 212 and theoff-gases 222 from the pyrolysis zone 214 are combined into one gasstream 224. Once carbonized, the carbonized biomass 225 exits thesecond/pyrolysis zone 214 and enters the third/temperature-reducing orcooling zone 216.

In one embodiment, when the carbonized biomass 225 enters the coolingzone 216, the carbonized biomass 225 is allowed to cool to a specifiedtemperature range of about 20° C. to 25° C. (about room temperature) tobecome temperature-reduced carbonized biomass 226, as discussed above.In various embodiments, the BPU 202 includes a plurality of coolingzones. In one embodiment, the cooling zone 216 cools the carbonizedbiomass to below 200° C. In one embodiment, the cooling zone includes amixer to agitate and uniformly cool the materials. In variousembodiments, one or more of the plurality of cooling zones is outside ofthe BPU 202.

As illustrated in FIGS. 2 and 5, the gas-phase separator unit 200includes at least one input and a plurality of outputs. In thisillustrative embodiment, the at least one input is connected to theexhaust ports on the first/preheat zone 212 and the second/pyrolysiszone 214 of the BPU 202. One of the outputs is connected to the carbonrecovery unit 500 (which is configured to enrich the material), andanother one of the outputs is connected to collection equipment orfurther processing equipment such as an acid hydrogenation unit 206 ordistillation column. In various embodiments, the gas-phase separatorprocesses the off-gases 220, 222 from the first/preheat zone 212 and thesecond/pyrolysis zone 214 to produce a condensate 228 and an enrichmentgas 204. In one embodiment, the condensate 228 includes polar compounds,such as acetic acid, methanol and furfural. In one embodiment, theenrichment gas 204 produced by the gas-phase separator 200 includes atleast non-polar gases. In one embodiment, the gas-phase separatorcomprises a fractionation column. In one embodiment, acetic acid is sentvia a line 228 to an optional acid hydrogenation unit 206. In anotherembodiment, methanol and/or furfural are sent via optional additionalline(s) 236 to a distillation/processing unit 238.

In the illustrated embodiments, the carbonized biomass exits the coolingreactor/zone along the material transfer unit 304 and enters the carbonrecovery unit 500. In various embodiments, as illustrated in more detailin FIG. 5 and discussed above, the carbon recovery unit 500 alsoincludes an input 524 connected to the gas-phase separator 200. In oneembodiment, the enrichment gas 204 is directed into the carbon recoveryunit 500 to be combined with the biogenic reagent 226 to create a highcarbon biogenic reagent 136. In another embodiment, a carbon-enrichedgas from an external source can also be directed to the carbon recoveryunit 500 to be combined with the biogenic reagent 226 to add additionalcarbon to the biogenic reagent. In various embodiments, gases pulledfrom the carbon recovery unit 500 at reference 234 are optionally usedin energy recovery systems and/or systems for further carbon enrichment.Similarly, in various embodiments, gases pulled from one or more zonesof the BPU 202 are optionally used in energy recovery systems and/orsystems for further carbon enrichment. Illustratively, the system 200can be co-located near a timber processing facility and carbon-enrichedgas from the timber processing facility can be used as gas from anexternal source.

Now referring generally to FIG. 3, one material feed system embodimentof the present disclosure is illustrated. As discussed above, highoxygen levels in the ambient air surrounding the raw material as itprocesses could result in undesirable combustion or oxidation of the rawmaterial, which reduces the amount and quality of the final product. Inone embodiment, the material feed system is a closed system and includesone or more manifolds configured to purge oxygen from the airsurrounding the raw material. In one embodiment, oxygen level of about0.5% to about 1.0% are used for pre-heating, pyrolyzing/carbonizing andcooling. It should be appreciated that a primary goal of the closedmaterial feed system is to reduce oxygen levels to not more than about3%, not more than about 2%, not more than about 1% or not more thanabout 0.5%. After the oxygen level is reduced, the biomass istransferred along the material feed system into the BPU. It should beappreciated that in various embodiments, pre-heating of inert gasesthrough recovered process energy and subsequent introduction ofpre-heated inert gases to the BPU, reactor or trimming reactor makes thesystem more efficient.

In some embodiments, a trimming reactor is included in the system. Inone trimming reactor embodiment, pyrolyzed material from the BPU is fedinto a separate additional reactor for further pyrolysis where heatedinert gas is introduced to create a product with higher fixed carbonlevels. In various embodiments, the secondary process may be conductedin a container such as a drum, tank, barrel, bin, tote, pipe, sack,press, or roll-off container. In various embodiments, the finalcontainer also may be used for transport of the carbonized biomass. Insome embodiments, the inert gas is heated via a heat exchanger thatderives heat from gases extracted from the BPU and combusted in aprocess gas heater.

As seen in FIG. 3, the closed material feed system 108 includes a rawmaterial feed hopper 300, a material transport unit 304 and an oxygenpurge manifold 302.

In one embodiment, the raw material feed hopper 300 is any suitableopen-air or closed-air container configured to receive raw orsized/dried biomass 109/209. The raw material feed hopper 300 isoperably connected with the material transport unit 304, which, in oneembodiment, is a screw or auger system operably rotated by a drivesource. In one embodiment, the raw material 109/209 is fed into thematerial transport unit 304 by a gravity-feed system. It should beappreciated that the material transport unit 304 of FIG. 3 is fashionedsuch that the screw or auger 305 is enclosed in a suitable enclosure307. In one embodiment, the enclosure 307 is substantially cylindricallyshaped. In various embodiments, material feed systems include a screw,auger, conveyor, drum, screen, chute, drop chamber, pneumatic conveyancedevice, including a rotary airlock or a double or triple flap airlock.

As the raw material 109/209 is fed from the raw material feed hopper 300to the material transport unit 304, the auger or screw 305 is rotated,moving the raw material 109/209 toward the oxygen purge manifold 302. Itshould be appreciated that, when the raw material 109/209 reaches theoxygen purge manifold 302, the ambient air among the raw material109/209 in the material transport unit 304 includes about 20.9% oxygen.In various embodiments, the oxygen purge manifold 302 is arrangedadjacent to or around the material transport unit 304. Within the oxygenfold manifold of one embodiment, the enclosure 307 of the materialtransport unit 304 includes a plurality of gas inlet ports 310 a, 310 b,310 c and a plurality of gas outlet ports 308 a, 308 b, 308 c.

The oxygen purge manifold 302 has at least one gas inlet line 312 and atleast one gas outlet line 314. In various embodiments, the at least onegas inlet line 312 of the oxygen purge manifold 302 is in operablecommunication with each of the plurality of gas inlet ports 310 a, 310b, 310 c. Similarly, in various embodiments, the at least one gas outletline 314 of the oxygen purge manifold 302 is in operable communicationwith each of the plurality of gas outlet ports 308 a, 308 b, 308 c. Itshould be appreciated that, in one embodiment, the gas inlet line 312 isconfigured to pump an inert gas into the gas inlet ports 310 a, 310 b,310 c. In one such embodiment, the inert gas is nitrogen containingsubstantially no oxygen. In one embodiment, the inert gas will flowcounter-current to the biomass.

As will be understood, the introduction of inert gas 312 into theenclosed material transport unit 304 will force the ambient air out ofthe enclosed system. In operation, when the inert gas 312 is introducedto the first gas inlet port 310 a of one embodiment, a quantity ofoxygen-rich ambient air is forced out of outlet port 308 a. It should beappreciated that, at this point, the desired level of not more thanabout 2% oxygen, not more than about 1% oxygen, not more than about 0.5%oxygen or not more than about 0.2% oxygen may not be achieved.Therefore, in various embodiments, additional infusions of the inert gas312 must be made to purge the requisite amount of oxygen from the airsurrounding the raw material 109 in the enclosed system. In oneembodiment, the second gas inlet port 310 b pumps the inert gas 312 intothe enclosed system subsequent to the infusion at the first gas inletport 310 a, thereby purging more of the remaining oxygen from theenclosed system. It should be appreciated that, after one or twoinfusions of inert gas 312 to purge the oxygen 314, the desired level ofless oxygen may be achieved. If, in one embodiment, the desired oxygenlevels are still not achieved after two inert gas infusions, a thirdinfusion of inert gas 312 at gas inlet 310 c will purge remainingundesired amounts of oxygen 314 from the enclosed system at gas outlet308 c. Additional inlets/outlets may also be incorporated if desired. Invarious embodiments, oxygen levels are monitored throughout the materialfeed system to allow calibration of the amount and location of inert gasinfusions.

In one alternative embodiment, heat, steam and gases recovered from thereactor are directed to the feed system where they are enclosed injacket and separated from direct contact with the feed material, butindirectly heat the feed material prior to introduction to the reactor.

In one alternative embodiment, heat, steam and gases recovered from thedrying zone of the reactor are directed to the feed system where theyare enclosed in jacket and separated from direct contact with the feedmaterial, but indirectly heat the feed material prior to introduction tothe reactor.

It should be appreciated that the gas inlet ports 310 a, 310 b, 310 cand the corresponding gas outlet ports 308 a, 308 b, 308 c,respectively, of one embodiment are slightly offset from one anotherwith respect to a vertical bisecting plane through the materialtransport unit 304. For example, in one embodiment, inlet port 310 a andcorresponding outlet port 308 a are offset on material transport unit304 by an amount that approximately corresponds with the pitch of theauger 305 in the material transport unit 304. In various embodiments,after the atmosphere surrounding the raw material 109/209 issatisfactorily de-oxygenated, it is fed from the material feed system108 into the BPU 102. In various embodiments, oxygen levels aremonitored throughout the material feed system to allow the calibrationof the amount and location of inert gas infusions.

It should be appreciated that, in one embodiment, the raw material109/209, and subsequently the dried biomass 221, preheated biomass123/223, carbonized biomass 125/225 and carbonized biomass 126/226,travel through the reactor 102 (or reactors) along a continuous materialtransport unit 304. In another embodiment, the material transport unitcarrying the material differs at different stages in the process. In oneembodiment, the process of moving the material through the reactor,zones or reactors is continuous. In one such embodiment, the speed ofthe material transport unit 304 is appropriately calibrated andcalculated by an associated controller and processor such that theoperation of the material transport unit 304 does not requireinterruption as the material moves through the reactor or reactors.

In another embodiment, the controller associated with the reactor 102 orreactors (112/114/116) is configured to adjust the speed of the materialtransport unit 304 based on one or more feedback sensors, detected gas(e.g. from the optional FTIR), measured parameters, temperature gauges,or other suitable variables in the reactor process. It should beappreciated that, in various embodiments, any suitable moisture sensors,temperature sensors or gas sensors in operable communication with thecontroller and processor could be integrated into or between each of thezones/reactors or at any suitable position along the material transportunit 304. In one embodiment, the controller and processor use theinformation from sensors or gauges to optimize the speed and efficiencyof the BPU 100/200. In one embodiment, the controller associated withthe reactor 102 or reactors (112/114/116) is configured to operate thematerial transport unit 304. In one embodiment, the controllerassociated with the reactor 102 or reactors (112/114/116) is configuredto monitor the concentration, temperature and moisture of the gas insidethe material transport unit 304 or inside any of the reactors. In oneembodiment, the controller is configured to adjust the speed of thematerial transport unit 304, the input of gases into the materialtransport unit and the heat applied to the material in the materialtransport unit based upon one or more readings taken by the varioussensors.

Referring now to FIGS. 2 and 4, one embodiment of the BPU 102 isillustrated. It should be appreciated that the graphical representationof the BPU 202 in FIG. 4 corresponds substantially to the BPU 202 inFIG. 2. It should also be appreciated that, in various embodiments, theBPU 202 is enclosed in a kiln shell to control and manipulate the highamounts of heat required for the reactor process. As seen in FIG. 4, inone embodiment, the kiln shell of the BPU 202 includes severalinsulating chambers (416, 418) surrounding the four zones 210, 212, 214and 216. In one embodiment, the kiln includes four separated zones. Invarious embodiments, each of the four zones 210, 212, 214 and 216 of theBPU 202 includes at least one inlet flight and at least one outletflight. As discussed in greater detail below, within each zone of onesuch embodiment, the inlet and outlet flights are configured to beadjustable to control the flow of feed material, gas and heat into andout of the zone. A supply of inert air can be introduced into the inletflight and the purged air can be extracted from the corresponding outletflight. In various embodiments, one or more of the outlet flights of azone in the BPU 202 are connected to one or more of the other inlet oroutlet flights in the BPU.

In one embodiment, after the raw material 209 is de-oxygenated in thematerial feed system 108, it is introduced to the BPU 202, andspecifically to the first of four zones the optional drying zone 210. Asseen in FIG. 4, the drying zone includes inlet flight 422 b and outletflight 420 a. In one embodiment, the drying zone is heated to atemperature of about 80° C. to about 150° C. to remove water or othermoisture from the raw materials 209. The biomass is then moved to thesecond or pre-heat zone 212 where the biomass is pre-heated as describedabove.

In another embodiment, the material that has optionally been dried andpre-heated is moved to the third or carbonization zone. In oneembodiment, carbonization occurs at a temperature from about 200° C. toabout 700° C., for example about 200° C., about 210° C., about 220° C.,about 230° C., about 240° C., about 250° C., about 260° C., about 270°C., about 280° C., about 290° C., about 300° C., about 310° C., about320° C., about 330° C., about 340° C., about 350° C., about 360° C.,about 370° C., about 380° C., about 390° C., about 400° C., 410° C.,about 420° C., about 430° C., about 440° C., about 450° C., about 460°C., about 470° C., about 480° C., about 490° C., about 500° C., about510° C., about 520° C., about 530° C., about 540° C., about 550° C.,about 560° C., about 570° C., about 580° C., about 590° C., about 600°C., about 610° C., about 620° C., about 630° C., about 640° C., about650° C., about 660° C., about 670° C., about 680° C., about 690° C., orabout 700° C. In another embodiment, a carbonization zone of a reactor421 is adapted to allow gases produced during carbonization to beextracted. In another embodiment, gases produced during carbonizationare extracted for optional later use. In one embodiment, a carbonizationtemperature is selected to minimize or eliminate production of methane(CH₄) and maximize carbon content of the carbonized biomass.

In another embodiment, carbonized biomass is moved to atemperature-reducing or cooling zone (third zone) and is allowed topassively cool or is actively cooled. In one embodiment, carbonizedbiomass solids are cooled to a temperature ±10, 20, 30 or 40° C. of roomtemperature.

In various embodiments, the BPU includes a plurality of gas introductionprobes and gas extraction probes. In the embodiment of the BPUillustrated in FIG. 4, the BPU further includes a plurality of gasintroduction probes: 408, 410, 412 and 414, and a plurality of gasextraction probes: 400, 402, 404 and 406. It should be appreciated that,in various embodiments, one of each gas introduction probes and one ofeach gas extraction probes correspond with a different one of theplurality of zones 210, 212, 214 and 216. It should also be appreciatedthat, in various alternative embodiments, the BPU 202 includes anysuitable number of gas introduction probes and gas extraction probes,including more than one gas introduction probes and more than one gasextraction probes for each of the plurality of zones.

In the illustrated embodiment, the drying zone 210 is associated withgas introduction probe 412 and gas extraction probe 402. In oneembodiment, the gas introduction probe 412 introduces nitrogen to thedrying zone 210 and the gas extraction probe 402 extracts gas from thedrying zone 210. It should be appreciated that, in various embodiments,the gas introduction probe 412 is configured to introduce a mixture ofgas into the drying zone 210. In one embodiment, the gas extracted isoxygen. It should be appreciated that, in various embodiments, the gasextraction probe 402 extracts gases from the drying zone 210 to bereused in a heat or energy recovery system, as described in more detailabove.

In the illustrated embodiment, the pre-heat zone 212 is associated withgas introduction probe 414 and gas extraction probe 400. In oneembodiment, gas introduction probe 414 introduces nitrogen to thepre-heat zone 212 and gas extraction probe 400 extracts gas from thepre-heat zone 212. It should be appreciated that, in variousembodiments, the gas introduction probe 414 is configured to introduce amixture of gas into the pre-heat zone 212. In various embodiments, thegas extracted in gas extraction probe 400 includes carbon-enrichedoff-gases. It should be appreciated that in one embodiment, as discussedabove, the gases extracted from the pre-heat zone 212 and pyrolysis zone214 are reintroduced to the material at a later stage in the process,for example in the carbon recovery unit. In various embodiments, thegases extracted from any of the zones of the reactor are used for eitherenergy recovery in the dryer or process gas heater, for furtherpyrolysis in a trimming reactor, or in the carbon enrichment unit.

In the illustrated embodiment, the pyrolysis zone 214 is associated withgas introduction probe 410 and gas extraction probe 404. In oneembodiment, gas introduction probe 410 introduces nitrogen to thepyrolysis zone 214 and gas extraction probe 404 extracts gas from thepyrolysis zone 214. It should be appreciated that, in variousembodiments, the gas introduction probe 410 is configured to introduce amixture of gas into the pyrolysis zone 214. In various embodiments, thegas extracted in the gas extraction probe 404 includes carbon-enrichedoff-gases. It should be appreciated that in one embodiment, as discussedabove, the carbon-enriched gases extracted from the pyrolysis zone 214are used and reintroduced to the material at a later stage in theprocess. In various embodiments, as described in more detail below, theextracted gas 400 from the pre-heat zone 212 and the extracted gas 404from the pyrolysis zone 214 are combined prior to being reintroduced tothe material.

In the illustrated embodiment, the cooling zone 116 is associated withgas introduction probe 408 and gas extraction probe 406. In oneembodiment, gas introduction probe 408 introduces nitrogen to thecooling zone116 and gas extraction probe 406 extracts gas from thecooling zone116. It should be appreciated that, in various embodiments,the gas introduction probe 408 is configured to introduce a mixture ofgas into the cooling zone116. It should be appreciated that, in variousembodiments, the gas extraction probe 406 extracts gases from thecooling zone116 to be reused in a heat or energy recovery system, asdescribed in more detail above.

It should be appreciated that the gas introduction probes and gasextraction probes of various embodiments described above are configuredto operate with the controller and plurality of sensors discussed aboveto adjust the levels and concentrations of gas being introduced to andgas being extracted from each zone.

In various embodiments, the gas introduction probes and gas extractionprobes are made of a suitable pipe configured to withstand hightemperature fluctuations. In one embodiment, the gas introduction probesand gas extraction probes include a plurality of openings through whichthe gas is introduced or extracted. In various embodiments, theplurality of openings are disposed on the lower side of the inlet andgas extraction probes. In various embodiments, each of the plurality ofopenings extends for a substantial length within the respective zone.

In one embodiment, the gas introduction probes extend from one side ofthe BPU 202 through each zone. In one such embodiment, each of the fourgas introduction probes extend from a single side of the BPU to each ofthe respective zones. In various embodiments, gaseous catalysts areadded that enrich fixed carbon levels. It should be appreciated that, insuch an embodiment, the plurality of openings for each of the four gasintroduction probes are only disposed in the respective zone associatedwith that particular gas introduction probe.

For example, viewing FIG. 4, if each of the gas introduction probesextends from the left side of the drying zone into each one of thezones, all four gas introduction probes would travel through the dryingzone, with the drying zone gas introduction probes terminating in thedrying zone. The three remaining gas introduction probes would alltravel through the pre-heat zone, with the pre-heat zone gasintroduction probe terminating in the pre-heat zone. The two remaininggas introduction probes would travel through the pyrolysis zone, withthe pyrolysis zone gas introduction probe terminating in the pyrolysiszone. The cooling zone gas introduction probe would be the only gasintroduction probe to travel into and terminate in the cooling zone. Itshould be appreciated that in various embodiments, the gas extractionprobes are configured similar to the gas introduction probes describedin this example. It should also be appreciated that the gas introductionprobes and gas extraction probes can each start from either side of theBPU.

In various embodiment, the gas introduction probes are arrangedconcentrically with one another to save space used by the multiple-portconfiguration described in the example above. In one such embodiment,each of the four inlet probes/ports would have a smaller diameter thanthe previous inlet probe/port. For example, in one embodiment, thedrying zone gas introduction probe has the largest interior diameter,and the pre-heat zone gas introduction probe is situated within theinterior diameter of the drying zone inlet probe/port, the pyrolysiszone gas introduction probe is then situated within the interiordiameter of the pre-heat zone gas introduction probe and the coolingzone gas introduction probe is situated within the pyrolysis zone gasintroduction probe. In one example embodiment, a suitable connector isattached to each of the four gas introduction probes outside of the BPU102 to control the air infused into each of the four gas introductionprobes individually.

In one such embodiment, similar to the example above, the drying zonegas introduction probe would terminate in the drying zone, and the threeother gas introduction probes would continue onto the preheat zone.However, with a concentric or substantially concentric arrangement, onlythe outer-most gas introduction probe is exposed in each zone beforebeing terminated. Therefore, in one such embodiment, the individual zonegas introductions are effectively controlled independent of one another,while only requiring one continuous gas introduction probe line. Itshould be appreciated that a similar concentric or substantiallyconcentric configuration is suitably used for the gas extraction probesin one embodiment.

In one embodiment, each zone or reactor is adapted to extract andcollect off-gases from one or more of the individual zones or reactors.In another embodiment, off-gases from each zone/reactor remain separatefor disposal, analysis and/or later use. In various embodiments, eachreactor/zone contains a gas detection system such as an FTIR that canmonitor gas formation within the zone/reactor. In another embodiment,off-gases from a plurality of zones/reactors are combined for disposal,analysis and/or later use, and in various embodiments, off gases fromone or more zones/reactors are fed to a process gas heater. In anotherembodiment, off-gases from one or more zones/reactors are fed into acarbon recovery unit. In another embodiment, off-gases from one or morezones/reactors are fed to a gas-phase separator prior to introduction inthe carbon recovery unit. In one embodiment, a gas-phase separatorcomprises a fractionation column. Any fractionation column known tothose skilled in the art may be used. In one embodiment, off-gases areseparated into non-polar compounds and polar compounds using a standardfractionation column heated to a suitable temperature, or a packedcolumn. In another embodiment, non-polar compounds or enriched gasesfrom a gas-phase separator are extracted for optional later use, and invarious embodiments, off gases from one or more zones/reactors are fedto a process gas heater. In one embodiment, gases extracted from thepre-heat zone/reactor, the pyrolysis zone/reactor and optionally thecooling zone/reactor are extracted into a combined stream and fed intothe gas-phase separator. In various embodiments, one or more of thezones/reactors is configured to control whether and how much gas isintroduced into the combined stream.

As discussed above and generally illustrated in FIG. 5, the off-gases124/224 from the BPU 102/202 are directed into the gas-phase separator200. In various embodiments, the off-gases 124/224 include the extractedgases 120 from the first/preheat zone/reactor 112/212 combined with theextracted gases 122/222 from the second/pyrolysis zone/reactor 114/214or either gas stream alone. When the off-gases 124/224 enter thegas-phase separator 200, the off-gases 124/224 are separated into polarcompounds 128/228/136/236 and non-polar compounds 204, such as non-polargases. In various embodiments, the gas-phase separator 200 is a knownfractionation column.

In various embodiments, the enriched gases 204 extracted from thecombined off-gases 124/224 are directed from the gas-phase separator 200into the carbon recovery unit 500 via input 524, which enriches thematerial. As discussed above, and as illustrated in FIGS. 8 and 11, itshould be appreciated that in various embodiments, the extracted gasesare first introduced into a material enrichment unit, and then into aseparate carbon recovery unit. In the embodiment illustrated in FIG. 5,the material enrichment takes place in the carbon recovery unit 500. Inone embodiment (FIG. 5), the gas-phase separator 200 includes aplurality of outputs. In various embodiments, one output from thegas-phase separator 200 is connected to the carbon recovery unit 500 tointroduce an enriched gas stream to the carbon recovery unit 500. In oneembodiment, a portion of the enriched gas stream is directed to thecarbon recovery unit 500 and another portion is directed to a scrubber,or another suitable purifying apparatus to clean and dispose of unwantedgas. In various embodiments, off-gases that are not sent to the carbonrecovery unit may be used for either energy recovery (for example in aprocess gas heater) or as an inert gas (for example in the deaerationunit, reactor, BPU, or cooler). Similarly, in various embodiments,off-gases from the carbon recovery unit may be used for either energyrecovery (for example in a process gas heater), as an inert gas (forexample in the deaeration unit, reactor, BPU, or cooler), or in asecondary recovery unit.

In one embodiment, another output from the gas-phase separator extractspolar compounds, optionally condensing them into a liquid component,including a plurality of different liquid parts. In various embodiments,the liquid includes water, acetic acid, methanol and furfural. Invarious embodiments, the outputted liquid is stored, disposed of,further processed, or re-used. For example, it should be appreciatedthat the water outputted in one embodiment can be re-used to heat orcool another portion of a system. In another embodiment, the water isdrained. It should also be appreciated that the acetic acid, methanoland furfural outputted in one embodiment can be routed to storage tanksfor re-use, re-sale, distillation or refinement.

As seen in FIG. 5, the carbon recovery unit 500 of one embodimentcomprises a housing with an upper portion and a lower portion. It shouldbe appreciated that, in various embodiments in which a materialenrichment unit is separate from the carbon recovery unit, the materialenrichment unit includes features similar to those discussed withrespect to the carbon recovery unit 500 of FIG. 5. In one embodiment,the carbon recovery unit, comprises: a housing 502 with an upper portion502 a and a lower portion 502 b; an inlet 524 at a bottom of the lowerportion of the housing configured to carry reactor off-gas; an outlet534 at a top of the upper portion of the housing configured to carry aconcentrated gas stream; a path 504 defined between the upper portionand lower portion of the housing; and a transport system 528 followingthe path, the transport system configured to transport reagent, whereinthe housing is shaped such that the reagent adsorbs at least some of thereactor off-gas. In various embodiments, the upper portion includes aplurality of outlets and the lower portion includes a plurality ofinlets.

In one embodiment, the housing 502 is substantially free of cornershaving an angle of 110 degrees or less, 90 degrees or less, 80 degreesor less or 70 degrees or less. In one embodiment, the housing 502 issubstantially free of convex corners. In another embodiment, the housing502 is substantially free of convex corners capable of producing eddiesor trapping air. In another embodiment, the housing 502 is substantiallyshaped like a cube, rectangular prism, ellipsoid, a stereographicellipsoid, a spheroid, two cones affixed base-to-base, two regulartetrahedrons affixed base-to-base, two rectangular pyramids affixedbase-to-base or two isosceles triangular prisms affixed base-to-base.

In one embodiment, the upper portion 502 a and lower portion 502 b ofthe housing 502 are each substantially shaped like a half-ellipsoid,half rectangular prism, half-stereographic ellipsoid, a half-spheroid, acone, a regular tetrahedron, a rectangular pyramid, an isoscelestriangular prism or a round-to-rectangular duct transition.

In another embodiment, the inlet 524 at the bottom of the lower portionof the housing 502 b and the outlet 534 at the top of the upper portionof the housing 502 a are configured to connect with a pipe. In anotherembodiment, the top of the lower portion of the housing 502 b and thebottom of the upper portion of the housing 502 a are substantiallyrectangular, circular or elliptical. In another embodiment, the widthbetween the top of the lower portion of the housing 502 b and the bottomof the upper portion of the housing 502 a is wider than a width of thetransport system 528. In one embodiment, the width of the transportsystem 528 is its height.

In one embodiment, the carbon recovery unit 500 comprises a path 504defined between the upper portion and the lower portion, an inletopening 506 and an outlet opening 508. In one embodiment, the inletopening and outlet opening are configured to receive the transportsystem. In one embodiment, the transport system 528 is at leastsemi-permeable or permeable to the enriching gas.

In one embodiment, the inlet opening 506 includes an inlet openingsealing mechanism to reduce escape of gas and the outlet opening 508includes an outlet opening sealing mechanism to reduce escape of gas. Inone embodiment, the inlet and outlet opening sealing mechanisms comprisean airlock.

In various embodiments, the lower portion 502 b of the housing of thecarbon recovery unit has a narrow round bottom connection opening, whichis connected to the gas-phase separator 200 for the transport of gasstream 204. In various embodiments, the top of the lower portion 502 bof the housing of the carbon recovery unit 500 is substantiallyrectangular in shape, and substantially wider than the narrow roundbottom connection opening. It should be appreciated that in oneembodiment, the lower portion transitions from the round bottom openingto a rectangular top opening. In one embodiment, the rectangular topopening of the lower portion is about six feet wide (along the directionof the conveyor system). In various embodiments, the top portion of thecarbon recovery unit 500 is shaped substantially similarly to the lowerportion. In one embodiment, the lower opening of the top portion iswider than the top opening of the lower portion. In one embodiment, therectangular lower opening of the top portion is about six and a halffeet wide (along the direction of the conveyor system). In oneembodiment, the top portion is configured to capture all gases passedthrough the carbon recovery unit 500 that are not adsorbed by theactivated materials.

It should be appreciated that, in various embodiments, the shape of thelower portion of the carbon recovery unit aids in slowing down anddispersing the gases 204 across a wider surface area of the conveyorcarrying the biogenic reagent 126/226. In various embodiments, theprecise shape of the lower 502 b and upper 502 a portions of the carbonrecovery unit 500 depend upon the angle of gas dispersion coming fromthe gas-phase separator pipe. It should be appreciated that in variousembodiments, the gas naturally will tend to expand as it is pumped up ata flared range of between 5 and 30 degrees from the vertical. In oneembodiment, the flare angle is approximately 15 degrees. It should beappreciated that the lower portion of the carbon recovery unit isconstructed with as few creases and corners as possible to prevent thetrapping of air or formation of eddies.

In one embodiment, the carbon recovery unit 500 is configured to connectto the gas-phase separator 200 as discussed above, as well as the BPU102/202. In various embodiments, the carbon recovery unit 500 isconnected to the output of the cooling reactor/zone 216/116, or the lastcooling zone of the BPU 102/202 or outside of the BPU. In oneembodiment, the output of the cooling reactor/zone 116/216 includesbiogenic reagent that have been processed in the BPU 102/202. In oneembodiment, the biogenic reagent 126/226 enter the carbon recovery unit500 along a suitable transport system. In various embodiments, the topportion and the bottom portion of the carbon recovery unit are connectedto one another, and define a pathway through which a transport systempasses. In one embodiment, the transport system is constructed with aporous or mesh material configured to allow gas to pass there through.It should be appreciated that the transport system is configured to passthrough an opening of the carbon recovery unit 500 and then through anexit opening in the carbon recovery. In some embodiments, the entranceand the exit into and out of the carbon recovery unit are appropriatelysealed with an airlock or another suitable sealing mechanism to preventgases from escaping through the conveyor opening. In variousembodiments, off-gases that are not sent to the carbon recovery unit maybe used for either energy recovery (for example in a process gas heater)or as an inert gas (for example in the deaeration unit, reactor, BPU, orcooler). Similarly, in various embodiments, off-gases from the carbonrecovery unit may be used for either energy recovery (for example in aprocess gas heater), as an inert gas (for example in the deaerationunit, reactor, BPU, or cooler), or in a secondary recovery unit.

In various embodiments, the process operates by first outputting thebiogenic reagent 126/226 from the cooling zone 116/216 onto thetransport system using a suitable discharge mechanism from the coolingreactor/zone 116/216. In one embodiment, the biogenic reagent 126/216are spread across the width of the transport system to minimize materialstacking or bunching and maximize surface area for gaseous absorption.At the point which the biogenic reagent 126/216 are deposited andsuitably spread onto the transport system, in various embodiments, thetransport system transports the biogenic reagent 126/216 through theopening in the carbon recovery unit 104 defined between the lowerportion and the top portion discussed above. In the carbon recovery unit104, the biogenic reagent 126/216 adsorb gases piped into the lowerportion of the carbon recovery unit 104 from the gas-phase separator200. After the biogenic reagent is enriched with non-polar gases, itshould be appreciated that the biogenic reagent becomes a high carbonbiogenic reagent. In various embodiments, the high carbon biogenicreagent is a final product of the process disclosed herein and istransported away from the carbon recovery unit 104 into a suitablestorage or post-processing apparatus.

In one embodiment, after the enriched gases 204 pass through theconveyor and the biogenic reagent 126/216, the resulting gas isextracted at the top portion of the carbon recovery unit 104. In variousembodiments, the exhausted gases 134 are carried away to a suitablescrubber, stack or recovery system. In some embodiments, the exhaustgases are exploited for any reusable qualities in the system, includingusage in a secondary carbon recovery unit or for energy. In variousembodiments, off-gases that are not sent to the carbon recovery unit maybe used for either energy recovery (for example in a process gas heater)or as an inert gas (for example in the deaeration unit, reactor, BPU, orcooler). Similarly, in various embodiments, off-gases from the carbonrecovery unit may be used for either energy recovery (for example in aprocess gas heater), as an inert gas (for example in the deaerationunit, reactor, BPU, or cooler), or in a secondary recovery unit.

It should be appreciated that the biogenic reagent 126/216 include ahigh amount of carbon, and carbon has a high preference for adsorbingnon-polar gases. It should also be appreciated that the enriched gasstream 204 includes primarily non-polar gases like terpenes, carbonmonoxide, carbon dioxide and methane. In various embodiments, as theenriched gases are directed from the gas-phase separator into the carbonrecovery unit, the gas flow rate and the conveyor speed are monitoredand controlled to ensure maximum absorption of the non-polar gases inthe biogenic reagent 126/216. In another embodiment, the high-energyorganic compounds comprise at least a portion of the enriched gases 204eluted during carbonization of the biomass, and outputted from thegas-phase separator 200 to the carbon recovery unit 104. In variousembodiments, the enriched gases 204 are further enriched with additionaladditives prior to being introduced to the carbon recovery unit ormaterial enrichment unit.

As discussed in more detail below, in various embodiments, the residencetime of the biogenic reagent 126/216 in the carbon recovery unit iscontrolled and varies based upon the composition of the biogenic reagent126/216 and gas flow and composition. In one embodiment, the biogenicreagent are passed through one or more carbon recovery units more thanone time. In various embodiments, the output of enriched air from thegas-phase separator and the output of exhausted air from the carbonrecovery unit 104 can be diverted or bifurcated into an additionalcarbon recovery unit or further refined or used for energy or inert gasfor use in the process.

Referring more generally to FIGS. 6 to 13, various embodiments of thepresent disclosure are illustrated and discussed. It should beappreciated that the various embodiments and alternatives discussedbelow with respect to FIGS. 6 to 13 apply to the embodiments of FIGS. 1to 5 discussed above, and vice versa.

Referring specifically now to FIG. 6, this embodiment can utilize a BPUincluding a single reactor having two to a greater plurality ofdifferent zones. Two zones are shown in the illustrative embodiment,however, any different number of zones could be employed. In oneembodiment, each zone is connected to at least one other zone via amaterial transport unit (not pictured). In one embodiment, the materialtransport unit controls atmosphere and temperature conditions.

Specifically in one embodiment illustrated in FIG. 6, the system 600includes a material feed system 602, a BPU 606 including a pyrolysiszone 608 and a cooling zone 610, a cooler 614 and a carbon recovery unit616. It should be appreciated that the cooler 614 of FIG. 6 is outsideof the BPU 606, and is in addition to the cooling zone 610 that resideswithin the BPU 606.

.In various embodiments, the system 600 includes an optional dryerbetween the material feed system 602 and the BPU 606. In variousembodiments, the BPU 606 includes a plurality of zones. In FIG. 6, theBPU 606 includes a pyrolysis zone 608 and a cooling zone 610. The BPU606 also includes at least a plurality of inlets and outlets for addingsubstances to and removing various substances from the plurality of zone608, 610, including at least condensable vapors and non-condensablegases 612. It should be appreciated that in various embodimentsdiscussed below, one or more of the plurality of zone 608 or 610 areenclosed by the BPU 606.

Referring now to FIG. 7, a system 700 of one embodiment is illustratedand discussed. System 700 includes a single-reactor system, including amaterial feed system 702, a pre-heater 706, a pyrolysis reactor 708, acooler, 714 and a carbon recovery unit 716. In various embodiments, thesystem 700 includes an optional dryer 704 between the material feedsystem 702 and the pre-heater 706. As seen in FIG. 7, the pyrolysisreactor 708 of one embodiment includes at least one gas inlet 710 and atleast one outlet 712 for outputting substances from the pyrolysisreactor 708. In various embodiments, the substances outputted throughoutlet 712 include condensable vapors and/or non-condensable gases. Itshould be appreciated that the pyrolysis reactor 708 can include one ormore zones, not discussed in detail herein. In various embodiments, thesystem 700 includes one or more reactors in addition to the pyrolysisreactor 708.

Referring now to FIG. 8, a single-reactor, multiple zone BPU system 800of one embodiment is illustrated and discussed. System 800 includes amaterial feed system 802, a BPU 808 having a pyrolysis zone 810 and acooling zone 812, a material enrichment unit 818, and a carbon recoveryunit 820. Similar to the embodiments discussed above, FIG. 8 alsoincludes an optional dryer 804 located between the material feed system802 and the BPU 808. It should be appreciated that moisture 806 from thedryer 804 is removed during the drying process. FIG. 8 also includes anoptional cooler 816 outside of the BPU 808 and before the materialenrichment unit 818. As discussed in more detail below, the materialenrichment unit 818 is in communication with a gas outlet 814 of the BPU808, which carries condensable vapors and non-condensable gases from theBPU. It should be appreciated that various embodiments illustrated inFIG. 8 include a separate carbon recovery unit 820 from the materialenrichment unit 818. As discussed above, in various embodiments, thecarbon recovery unit 820 of FIG. 8 is an appropriate vessel in which theenriched material is stored following the material enrichment unit 818,and the carbon recovery unit 820 does not further enrich the material.

It should be appreciated that, in various embodiments, an optionalprocess gas heater 824 is disposed in the system and attached to the BPU808. In various embodiments, vapors or other off-gases from the BPU 808are inputted into the optional process gas heater 824, along with anexternal source of any one or more of air, natural gas, and nitrogen. Asdiscussed below, in various embodiments, the air emissions from theprocess gas heater 824 are inputted into dryer 804 as a heat or energyrecovery system.

Referring now to FIG. 9, a BPU 908 of a system 900 of one embodiment isillustrated and discussed. The BPU 908 includes a plurality of zones:the pre-heat zone 904, the pyrolysis zone 910, and the cooling zone 914.The BPU 908 of one embodiment also includes a material feed system 902in communication with one of the zones at least one gas inlet 906 incommunication with one or more of the zones 904, 910, 914. In variousembodiments, as discussed below, one of the zones also includes at leastone outlet 912 for outputting substances, in one embodiment, condensablevapors and/or non-condensable gases. In various embodiments, one of thezones also includes an outlet for outputting the advanced carbon fromthe system 900.

It should be appreciated that, although FIG. 9 shows the gas inlet 906being connected to the pre-heat zone 904, various embodiments includeinlets into any combination of the three zones. Similarly, it should beappreciated that although the gaseous outlet 912 comes from thepyrolysis zone 910, various embodiments include outlets out of one ormore of any combination of the three zones. As discussed below, variousembodiments contemplated include inputs and outputs within the BPU:e.g., an outlet of the pyrolysis zone 910 is then input into thepre-heat zone 904. It should be appreciated that, in the illustratedembodiment, each of the reactors in the BPU is connected to one anothervia the material feed system, as discussed above.

In various embodiments, the pre-heat zone 904 of the BPU 908 isconfigured for feeding biomass 902 (or another carbon-containingfeedstock) in a manner that does not “shock” the biomass, which wouldrupture the cell walls and initiate fast decomposition of the solidphase into vapors and gases. In one embodiment, pre-heat zone 904 can bethought of as mild pyrolysis.

In various embodiments, pyrolysis zone 910 of the BPU 908 is configuredas the primary reaction zone, in which preheated material undergoespyrolysis chemistry to release gases and condensable vapors, resultingin a solid material which is a high-carbon reaction intermediate.Biomass components (primarily cellulose, hemicellulose, and lignin)decompose and create vapors, which escape by penetrating through poresor creating new nanopores. The latter effect contributes to the creationof porosity and surface area.

In various embodiments, the cooling zone 914 of the BPU 908 isconfigured for receiving the high-carbon reaction intermediate andcooling down the solids, i.e. the cooling zone 914 will be a lowertemperature than the pyrolysis zone 910. In the cooling zone 914, thechemistry and mass transport can be complex. In various embodiments,secondary reactions occur in the cooling zone 914. It should beappreciated that carbon-containing components that are in the gas phasecan decompose to form additional fixed carbon and/or become adsorbedonto the carbon. Thus, the advanced carbon 916 is not simply the solid,devolatilized residue of the processing steps, but rather includesadditional carbon that has been deposited from the gas phase, such as bydecomposition of organic vapors (e.g., tars) that can form carbon.

Referring now to FIGS. 10 to 13, various multiple reactor embodiments ofthe system are illustrated and discussed. Similar to each of theembodiments, the systems include an optional deaerator and an optionaldryer, as discussed in more detail below. Referring to FIG. 10, thesystem 1000 includes material feed system 1002, a pyrolysis reactor1012, a cooling reactor 1018, a cooler 1020 and a carbon recovery unit1022. As discussed further below, a gas source 1016 is configured toinput gas into one or both of the pyrolysis reactor 1012 and the coolingreactor 1018. In various embodiments, the pyrolysis reactor includes anoutlet to output at least condensable vapors and/or non-condensablegases. In various embodiments, the carbon recovery unit 1022 includes anoutlet 1024 to output activated carbon from the system 1000.

It should be appreciated that, in various embodiments illustrated atleast in FIGS. 10 to 13, the illustrated systems includes an optionalde-aerator and an optional dryer. As seen in FIG. 10, for example,represented by broken lines, the optional de-aerator 1004 is connectedto the system 1000 between the material feed system 1002 and thepyrolysis reactor 1002. Similarly, the dryer 1006 is connected to thesystem 1000 between the material feed system 1002 and the pyrolysisreactor 1012. In various embodiments, the dryer 1006 and deaerator 1004are also connected to one another such that the material from thematerial feed system can follow any number of different paths throughthe material feed system, the de-aerator, the dryer, and to thepyrolysis reactor. It should be appreciated that in some embodiments,the material only passes through one of the optional de-aerator 1004 anddryer 1006.

In some embodiments, with reference to FIG. 10, a process for producinga high-carbon biogenic reagent comprises the following steps:

(a) providing a carbon-containing feedstock comprising biomass;

(b) optionally drying the feedstock to remove at least a portion ofmoisture contained within the feedstock;

(c) optionally deaerating the feedstock to remove at least a portion ofinterstitial oxygen, if any, contained with the feedstock;

(d) pyrolyzing the feedstock in the presence of a substantially inertgas phase for at least 10 minutes and with at least one temperatureselected from about 250° C. to about 700° C., to generate hot pyrolyzedsolids, condensable vapors, and non-condensable gases;

(e) separating at least a portion of the condensable vapors and at leasta portion of the non-condensable gases from the hot pyrolyzed solids;

(f) cooling the hot pyrolyzed solids to generate cooled pyrolyzedsolids; and

(g) recovering a high-carbon biogenic reagent comprising at least aportion of the cooled pyrolyzed solids.

Referring now to FIG. 11 a multiple reactor system 1100 of oneembodiment is illustrated. Similar to the embodiment discussed above andillustrated in FIG. 10, this embodiment includes a material feed system1102, pyrolysis reactor 1112, cooling reactor 1118, and carbon recoveryunit 1124. In the illustrated embodiment of FIG. 11, the cooler 1120 isoptional, and a material enrichment unit 1122 is disposed between theoptional cooler 1120 and the carbon recovery unit 1124. It should beappreciated that, in various embodiments, the material enrichment unit1122 enriches the material before it continues into the separate carbonrecovery unit 1124, which may or may not further enrich the material. Invarious embodiments, an optional deaerator 1104 and an optional dryer1106 are disposed between the material feed system 1102 and thepyrolysis reactor 1112. In the illustrated embodiment, the pyrolysisreactor 1112 also includes an outlet 1114 configured to removesubstances such as condensable vapors and non-condensable gases, androute the removed substances to the material enrichment unit 1122.

Various embodiments extend the concept of additional carbon formation byincluding a separate material enrichment unit 818, 1122 in which cooledcarbon is subjected to an environment including carbon-containingspecies, to enrich the carbon content of the final product. When thetemperature of this unit is below pyrolysis temperatures, the additionalcarbon is expected to be in the form of adsorbed carbonaceous species,rather than additional fixed carbon.

As will be described in detail below, there are a large number ofoptions as to intermediate input and output (purge or probe) streams ofone or more phases present in any particular reactor, various mass andenergy recycle schemes, various additives that may be introducedanywhere in the process, adjustability of process conditions includingboth reaction and separation conditions in order to tailor productdistributions, and so on. Zone or reactor-specific input and outputstreams enable good process monitoring and control, such as through FTIRsampling and dynamic process adjustments.

The present disclosure is different than fast pyrolysis, and it isdifferent than conventional slow pyrolysis. High-quality carbonmaterials in the present disclosure, including compositions with highfractions of fixed carbon, may be obtained from the disclosed processesand systems.

“Biomass,” for purposes of this disclosure, shall be construed as anybiogenic feedstock or mixture of a biogenic and non-biogenic feedstock.Elementally, biomass includes at least carbon, hydrogen, and oxygen. Themethods and apparatus of the invention can accommodate a wide range offeedstocks of various types, sizes, and moisture contents.

Biomass includes, for example, plant and plant-derived material,vegetation, agricultural waste, forestry waste, wood waste, paper waste,animal-derived waste, poultry-derived waste, and municipal solid waste.In various embodiments of the invention utilizing biomass, the biomassfeedstock may include one or more materials selected from: timberharvesting residues, softwood chips, hardwood chips, tree branches, treestumps, knots, leaves, bark, sawdust, off-spec paper pulp, cellulose,corn, corn stover, wheat straw, rice straw, sugarcane bagasse,switchgrass, miscanthus, animal manure, municipal garbage, municipalsewage, commercial waste, grape pumice, almond shells, pecan shells,coconut shells, coffee grounds, grass pellets, hay pellets, woodpellets, cardboard, paper, carbohydrates, plastic, and cloth. A personof ordinary skill in the art will readily appreciate that the feedstockoptions are virtually unlimited.

Various embodiments of the present disclosure are also be used forcarbon-containing feedstocks other than biomass, such as a fossil fuel(e.g., coal or petroleum coke), or any mixtures of biomass and fossilfuels (such as biomass/coal blends). In some embodiments, a biogenicfeedstock is, or includes, coal, oil shale, crude oil, asphalt, orsolids from crude-oil processing (such as petcoke). Feedstocks mayinclude waste tires, recycled plastics, recycled paper, and other wasteor recycled materials. Any method, apparatus, or system described hereinmay be used with any carbonaceous feedstock. Carbon-containingfeedstocks may be transportable by any known means, such as by truck,train, ship, barge, tractor trailer, or any other vehicle or means ofconveyance.

Selection of a particular feedstock or feedstocks is not regarded astechnically critical, but is carried out in a manner that tends to favoran economical process. Typically, regardless of the feedstocks chosen,there can be (in some embodiments) screening to remove undesirablematerials. The feedstock can optionally be dried prior to processing.

The feedstock employed may be provided or processed into a wide varietyof particle sizes or shapes. For example, the feed material may be afine powder, or a mixture of fine and coarse particles. The feedmaterial may be in the form of large pieces of material, such as woodchips or other forms of wood (e.g., round, cylindrical, square, etc.).In some embodiments, the feed material comprises pellets or otheragglomerated forms of particles that have been pressed together orotherwise bound, such as with a binder.

It is noted that size reduction is a costly and energy-intensiveprocess. Pyrolyzed material can be sized with significantly less energyinput, i.e. it can be more energy efficient to reduce the particle sizeof the product, not the feedstock. This is an option in the presentdisclosure because the process does not require a fine startingmaterial, and there is not necessarily any particle-size reductionduring processing. The present disclosure provides the ability toprocess very large pieces of feedstock. Notably, many marketapplications of the high-carbon product actually require large sizes(e.g., on the order of centimeters), so that in some embodiments, largepieces are fed, produced, and sold. It should be appreciated that, whilenot necessary in all embodiments of this disclosure, smaller sizing hasresulted in higher fixed carbon numbers under similar process conditionsand may be preferred in some embodiments.

When it is desired to produce a final carbonaceous biogenic reagent thathas structural integrity, such as in the form of cylinders, there are atleast two options in the context of this invention. First, the materialproduced from the process is collected and then further processmechanically into the desired form. For example, the product is pressedor pelletized, with a binder. The second option is to utilize feedmaterials that generally possess the desired size and/or shape for thefinal product, and employ processing steps that do not destroy the basicstructure of the feed material. In some embodiments, the feed andproduct have similar geometrical shapes, such as spheres, cylinders, orcubes.

The ability to maintain the approximate shape of feed materialthroughout the process is beneficial when product strength is important.Also, this control avoids the difficulty and cost of pelletizing highfixed-carbon materials.

The starting feed material in various embodiments is provided with arange of moisture levels, as will be appreciated. In some embodiments,the feed material is already sufficiently dry that it need not befurther dried before pyrolysis. Typically, it will be desirable toutilize commercial sources of biomass which will usually containmoisture, and feed the biomass through a drying step before introductioninto the pyrolysis reactor. However, in some embodiments a driedfeedstock is used. It should be appreciated that, in variousembodiments, while any biomass works, the following factors may impactthe process and its products: how material is grown, harvested,irrigated, material species selection and carbon content. Particularly,in various embodiments, low fertilizer and low phosphorous used ingrowing results in better properties for metal making. In variousembodiments, low impact shearing during harvest results in greaterstrength. In various embodiments, less irrigation and smaller growthrings may result in greater strength.

It should be appreciated that, in various embodiments additives and/orcatalysts are included in the BPU, and temperature profiles within theBPU are selected to promote production of carbon dioxide over carbonmonoxide, leading to greater fixed carbon in the final product.

It is desirable to provide a relatively low-oxygen environment in thepyrolysis reactor, such as about 10 wt %, 5 wt %, 3 wt %, or 1 wt % O₂in the gas phase. First, uncontrolled combustion should be avoided inthe pyrolysis reactor, for safety reasons. Some amount of total carbonoxidation to CO₂ may occur, and the heat released from the exothermicoxidation may assist the endothermic pyrolysis chemistry. Large amountsof oxidation of carbon, including partial oxidation to syngas, willreduce the carbon yield to solids.

Practically speaking, it can be difficult to achieve a strictlyoxygen-free environment in each of the reactor(s) or the BPU. This limitcan be approached, and in some embodiments, the reactor(s) or the BPU issubstantially free of molecular oxygen in the gas phase. To ensure thatlittle or no oxygen is present in the reactor(s) or BPU, it may bedesirable to remove air from the feed material before it is introducedto the reactor(s) or the BPU. There are various ways to remove or reduceair in the feedstock.

In some embodiments, as seen in FIGS. 10, 11, 12 and 13, a deaerationunit is utilized in which feedstock, before or after drying, is conveyedin the presence of another gas which can remove adsorbed oxygen andpenetrate the feedstock pores to remove oxygen from the pores. Mostgases that have lower than 21 vol % O₂ may be employed, at varyingeffectiveness. In some embodiments, nitrogen is employed. In someembodiments, CO and/or CO₂ is employed. Mixtures may be used, such as amixture of nitrogen and a small amount of oxygen. Steam may be presentin the deaeration gas, although adding significant moisture back to thefeed should be avoided. The effluent from the deaeration unit may bepurged (to the atmosphere or to an emissions treatment unit) orrecycled.

In principle, the effluent (or a portion thereof) from the deaerationunit could be introduced into the pyrolysis reactor itself since theoxygen removed from the solids will now be highly diluted. In thisembodiment, it may be advantageous to introduce the deaeration effluentgas to the last zone of the reactor, when it is operated in acountercurrent configuration.

Various types of deaeration units may be employed. In one embodiment, ifdrying it to be performed, deaerating after drying prevents the step ofscrubbing soluble oxygen out of the moisture present. In certainembodiments, the drying and deaerating steps are combined into a singleunit, or some amount of deaeration is achieved during drying.

The optionally dried and optionally deaerated feed material isintroduced to a pyrolysis reactor or multiple reactors in series orparallel. The material feed system in various embodiments introduces thefeedstock using any known means, including screw material feed systemsor lock hoppers, for example. In some embodiments, a material feedsystem incorporates an airlock.

When a single reactor is employed (such as in FIG. 6, 3 or 4), multiplezones can be present. Multiple zones, such as two, three, four, or morezones, can allow for the separate control of temperature, solidsresidence time, gas residence time, gas composition, flow pattern,and/or pressure in order to adjust the overall process performance.

As discussed above, references to “zones” shall be broadly construed toinclude regions of space within a single physical unit (such as in FIG.6, 8 or 9), physically separate units (such as in FIGS. 7 and 10 to 13),or any combination thereof. For a BPU, the demarcation of zones withinthat BPU may relate to structure, such as the presence of flights withinthe BPU or distinct heating elements to provide heat to separate zones.Alternatively, or additionally, in various embodiments, the demarcationof zones in a BPU relates to function, such as at least: distincttemperatures, fluid flow patterns, solid flow patterns, and extent ofreaction. In a single batch reactor, “zones” are operating regimes intime, rather than in space. Various embodiments include the use ofmultiple batch BPUs.

It will be appreciated that there are not necessarily abrupt transitionsfrom one zone to another zone. For example, the boundary between thepreheating zone and pyrolysis zone may be somewhat arbitrary; someamount of pyrolysis may take place in a portion of the preheating zone,and some amount of “preheating” may continue to take place in thepyrolysis zone. The temperature profile in the BPU is typicallycontinuous, including at zone boundaries within the zone.

Some embodiments, as seen for example in FIG. 9, employ a pre-heat zone304 that is operated under conditions of preheating and/or mildpyrolysis. In various embodiments, the temperature of the pre-heat zone304 is from about 80° C. to about 500° C., such as about 300° C. toabout 400° C. In various embodiments, the temperature of the pre-heatzone 304 is not so high as to shock the biomass material which rupturesthe cell walls and initiates fast decomposition of the solid phase intovapors and gases. Pyrolysis commonly known as fast or flash pyrolysis isavoided in the present disclosure.

All references to zone temperatures in this specification should beconstrued in a non-limiting way to include temperatures that may applyto the bulk solids present, or the gas phase, or the reactor or BPUwalls (on the process side). It will be understood that there will be atemperature gradient in each zone, both axially and radially, as well astemporally (i.e., following start-up or due to transients). Thus,references to zone temperatures may be references to averagetemperatures or other effective temperatures that may influence theactual kinetics. Temperatures may be directly measured by thermocouplesor other temperature probes, or indirectly measured or estimated byother means.

The second zone, or the primary pyrolysis zone, is operated underconditions of pyrolysis or carbonization. The temperature of thepyrolysis zone may be selected from about 250° C. to about 700° C., suchas about 300° C., 350° C., 400° C., 450° C., 500° C., 550° C., 600° C.,or 650° C. Within this zone, preheated biomass undergoes pyrolysischemistry to release gases and condensable vapors, leaving a significantamount of solid material as a high-carbon reaction intermediate. Biomasscomponents (primarily cellulose, hemicellulose, and lignin) decomposeand create vapors, which escape by penetrating through pores or creatingnew pores. The temperature will at least depend on the residence time ofthe pyrolysis zone, as well as the nature of the feedstock and productproperties.

The cooling zone is operated to cool down the high-carbon reactionintermediate to varying degrees. In various embodiments, the temperatureof the cooling zone is a lower temperature than that of the pyrolysiszone. In various embodiments, the temperature of the cooling zone isselected from about 100° C. to about 550° C., such as about 150° C. toabout 350° C.

In various embodiments, chemical reactions continue to occur in thecooling zone. It should be appreciated that in various embodiments,secondary pyrolysis reactions are initiated in the cooling zone.Carbon-containing components that are in the gas phase can condense (dueto the reduced temperature of the cooling zone). The temperature remainssufficiently high, however, to promote reactions that may formadditional fixed carbon from the condensed liquids (secondary pyrolysis)or at least form bonds between adsorbed species and the fixed carbon.One exemplary reaction that may take place is the conversion of carbonmonoxide to carbon dioxide plus fixed carbon (Boudouard reaction).

The residence times of the zones may vary. For a desired amount ofpyrolysis, higher temperatures may allow for lower reaction times, andvice versa. The residence time in a continuous BPU (reactor) is thevolume divided by the volumetric flow rate. The residence time in abatch reactor is the batch reaction time, following heating to reactiontemperature.

It should be recognized that in multiphase BPUs, there are multipleresidence times. In the present context, in each zone, there will be aresidence time (and residence-time distribution) of both the solidsphase and the vapor phase. For a given apparatus employing multiplezones, and with a given throughput, the residence times across the zoneswill generally be coupled on the solids side, but residence times may beuncoupled on the vapor side when multiple inlet and outlet ports areutilized in individual zones. in various embodiments, the solids andvapor residence times are uncoupled.

The solids residence time of the preheating zone may be selected fromabout 5 min to about 60 min, such as about 10 min depending on thetemperature and time required to reach a preheat temperature. Theheat-transfer rate, which will depend on the particle type and size, thephysical apparatus, and on the heating parameters, will dictate theminimum residence time necessary to allow the solids to reach apredetermined preheat temperature.

The solids residence time of the pyrolysis zone may be selected fromabout 10 min to about 120 min, such as about 20 min, 30 min, or 45 min.Depending on the pyrolysis temperature in this zone, there should besufficient time to allow the carbonization chemistry to take place,following the necessary heat transfer. For times below about 10 min, inorder to remove high quantities of non-carbon elements, the temperaturewould need to be quite high, such as above 700° C. This temperaturewould promote fast pyrolysis and its generation of vapors and gasesderived from the carbon itself, which is to be avoided when the intendedproduct is solid carbon.

In a static system of various embodiments, an equilibrium conversion isreached at a certain time. When, as in certain embodiments, vapor iscontinuously flowing over solids with continuous volatiles removal, theequilibrium constraint may be removed to allow for pyrolysis anddevolatilization to continue until reaction rates approach zero. Longertimes would not tend to substantially alter the remaining recalcitrantsolids.

The solids residence time of the cooling zone in various embodiments maybe selected from about 5 min to about 60 min, such as about 30 min.Depending on the cooling temperature in this zone, there should besufficient time to allow the carbon solids to cool to the desiredtemperature. The cooling rate and temperature will dictate the minimumresidence time necessary to allow the carbon to be cooled. Additionaltime may not be desirable, unless some amount of secondary pyrolysis isdesired.

As discussed above, the residence time of the vapor phase may beseparately selected and controlled. The vapor residence time of thepreheating zone may be selected from about 0.1 min to about 10 min, suchas about 1 min. The vapor residence time of the pyrolysis zone may beselected from about 0.1 min to about 20 min, such as about 2 min. Thevapor residence time of the cooling zone may be selected from about 0.1min to about 15 min, such as about 1.5 min. Short vapor residence timespromote fast sweeping of volatiles out of the system, while longer vaporresidence times promote reactions of components in the vapor phase withthe solid phase.

The mode of operation for the reactor, and overall system, may becontinuous, semi-continuous, batch, or any combination or variation ofthese. In some embodiments, the BPU is a continuous, countercurrentreactor in which solids and vapor flow substantially in oppositedirections. The BPU may also be operated in batch but with simulatedcountercurrent flow of vapors, such as by periodically introducing andremoving gas phases from the batch vessel.

Various flow patterns may be desired or observed. With chemicalreactions and simultaneous separations involving multiple phases inmultiple zones , the fluid dynamics can be quite complex. Typically, theflow of solids may approach plug flow (well-mixed in the radialdimension) while the flow of vapor may approach fully mixed flow (fasttransport in both radial and axial dimensions). Multiple inlet andoutlet ports for vapor may contribute to overall mixing.

The pressure in each zone may be separately selected and controlled. Thepressure of each zone may be independently selected from about 1 kPa toabout 3000 kPa, such as about 101.3 kPa (normal atmospheric pressure).Independent zone control of pressure is possible when multiple gasinlets and outlets are used, including vacuum ports to withdraw gas whena zone pressure less than atmospheric is desired. Similarly, in amultiple reactor system, the pressure in each reactor may beindependently selected and controlled.

The process may conveniently be operated at atmospheric pressure, insome embodiments. There are many advantages associated with operation atatmospheric pressure, ranging from mechanical simplicity to enhancedsafety. In certain embodiments, the pyrolysis zone is operated at apressure of about 90 kPa, 95 kPa, 100 kPa, 101 kPa, 102 kPa, 105 kPa, or110 kPa (absolute pressures).

Vacuum operation (e.g., 10-100 kPa) would promote fast sweeping ofvolatiles out of the system. Higher pressures (e.g., 100-1000 kPa) maybe useful when the off-gases will be fed to a high-pressure operation.Elevated pressures may also be useful to promote heat transfer,chemistry, or separations.

The step of separating at least a portion of the condensable vapors andat least a portion of the non-condensable gases from the hot pyrolyzedsolids may be accomplished in the reactor itself, or using a distinctseparation unit. A substantially inert sweep gas may be introduced intoone or more of the zones. Condensable vapors and non-condensable gasesare then carried away from the zone (s) in the sweep gas, and out of theBPU.

The sweep gas may be N₂, Ar, CO, CO₂, H₂, H₂O, CH₄, other lighthydrocarbons, or combinations thereof, for example. The sweep gas mayfirst be preheated prior to introduction, or possibly cooled if it isobtained from a heated source.

The sweep gas more thoroughly removes volatile components, by gettingthem out of the system before they can condense or further react. Thesweep gas allows volatiles to be removed at higher rates than would beattained merely from volatilization at a given process temperature. Or,use of the sweep gas allows milder temperatures to be used to remove acertain quantity of volatiles. The reason the sweep gas improves thevolatiles removal is that the mechanism of separation is not merelyrelative volatility but rather liquid/vapor phase disengagement assistedby the sweep gas. The sweep gas can both reduce mass-transferlimitations of volatilization as well as reduce thermodynamiclimitations by continuously depleting a given volatile species, to causemore of it to vaporize to attain thermodynamic equilibrium.

It is important to remove gases laden with volatile organic carbon fromsubsequent processing stages, in order to produce a product with highfixed carbon. Without removal, the volatile carbon can adsorb or absorbonto the pyrolyzed solids, thereby requiring additional energy (cost) toachieve a purer form of carbon which may be desired. By removing vaporsquickly, it is also speculated that porosity may be enhanced in thepyrolyzing solids. In various embodiments, such as activated carbonproducts, higher porosity is desirable.

In certain embodiments, the sweep gas in conjunction with a relativelylow process pressure, such as atmospheric pressure, provides for fastvapor removal without large amounts of inert gas necessary.

In some embodiments, the sweep gas flows countercurrent to the flowdirection of feedstock. In other embodiments, the sweep gas flowscocurrent to the flow direction of feedstock. In some embodiments, theflow pattern of solids approaches plug flow while the flow pattern ofthe sweep gas, and gas phase generally, approaches fully mixed flow inone or more zones.

The sweep may be performed in any one or more of the zones. In someembodiments, the sweep gas is introduced into the cooling zone andextracted (along with volatiles produced) from the cooling and/orpyrolysis zones. In some embodiments, the sweep gas is introduced intothe pyrolysis zone and extracted from the pyrolysis and/or preheatingzones. In some embodiments, the sweep gas is introduced into thepreheating zone and extracted from the pyrolysis zone. In these or otherembodiments, the sweep gas may be introduced into each of thepreheating, pyrolysis, and cooling zones and also extracted from each ofthe zones.

In some embodiments, the zone or zones in which separation is carriedout is a physically separate unit from the BPU. The separation unit orzone may be disposed between zones, if desired. For example, there maybe a separation unit placed between pyrolysis and cooling zones.

The sweep gas may be introduced continuously, especially when the solidsflow is continuous. When the pyrolysis reaction is operated as a batchprocess, the sweep gas may be introduced after a certain amount of time,or periodically, to remove volatiles. Even when the pyrolysis reactionis operated continuously, the sweep gas may be introducedsemi-continuously or periodically, if desired, with suitable valves andcontrols.

The volatiles-containing sweep gas may exit from the one or more zones,and may be combined if obtained from multiple zones. The resulting gasstream, containing various vapors, may then be fed to a process gasheater for control of air emissions, as discussed above and illustratedin FIG. 8. Any known thermal-oxidation unit may be employed. In someembodiments, the process gas heater is fed with natural gas and air, toreach sufficient temperatures for substantial destruction of volatilescontained therein.

The effluent of the process gas heater will be a hot gas streamcomprising water, carbon dioxide, and nitrogen. This effluent stream maybe purged directly to air emissions, if desired. In some embodiments,the energy content of the process gas heater effluent is recovered, suchas in a waste-heat recovery unit. The energy content may also berecovered by heat exchange with another stream (such as the sweep gas).The energy content may be utilized by directly or indirectly heating, orassisting with heating, a unit elsewhere in the process, such as thedryer or the reactor. In some embodiments, essentially all of theprocess gas heater effluent is employed for indirect heating (utilityside) of the dryer. The process gas heater may employ other fuels thannatural gas.

The yield of carbonaceous material may vary, depending on theabove-described factors including type of feedstock and processconditions. In some embodiments, the net yield of solids as a percentageof the starting feedstock, on a dry basis, is at least 25%, 30%, 35%,40%, 45%, 50%, or higher. The remainder will be split betweencondensable vapors, such as terpenes, tars, alcohols, acids, aldehydes,or ketones; and non-condensable gases, such as carbon monoxide,hydrogen, carbon dioxide, and methane. The relative amounts ofcondensable vapors compared to non-condensable gases will also depend onprocess conditions, including the water present.

In terms of the carbon balance, in some embodiments the net yield ofcarbon as a percentage of starting carbon in the feedstock is at least25%, 30%, 40%, 50%, 60%, 70%, or higher. For example, the in someembodiments the carbonaceous material contains between about 40% andabout 70% of the carbon contained in the starting feedstock. The rest ofthe carbon results in the formation of methane, carbon monoxide, carbondioxide, light hydrocarbons, aromatics, tars, terpenes, alcohols, acids,aldehydes, or ketones, to varying extents.

In alternative embodiments, some portion of these compounds is combinedwith the carbon-rich solids to enrich the carbon and energy content ofthe product. In these embodiments, some or all of the resulting gasstream from the reactor, containing various vapors, may be condensed, atleast in part, and then passed over cooled pyrolyzed solids derived fromthe cooling zone and/or from the separate cooler. These embodiments aredescribed in more detail below.

Following the reaction and cooling within the cooling zone (if present),the carbonaceous solids may be introduced into a cooler. In someembodiments, solids are collected and simply allowed to cool at slowrates. If the carbonaceous solids are reactive or unstable in air, itmay be desirable to maintain an inert atmosphere and/or rapidly cool thesolids to, for example, a temperature less than 40° C., such as ambienttemperature. In some embodiments, a water quench is employed for rapidcooling. In some embodiments, a fluidized-bed cooler is employed. A“cooler” should be broadly construed to also include containers, tanks,pipes, or portions thereof. It should be appreciated that in variousembodiments, the cooler is distinct from the cooling unit or coolingreactor.

In some embodiments, the process further comprises operating the coolerto cool the warm pyrolyzed solids with steam, thereby generating thecool pyrolyzed solids and superheated steam; wherein the drying iscarried out, at least in part, with the superheated steam derived fromthe cooler. Optionally, the cooler may be operated to first cool thewarm pyrolyzed solids with steam to reach a first cooler temperature,and then with air to reach a second cooler temperature, wherein thesecond cooler temperature is lower than the first cooler temperature andis associated with a reduced combustion risk for the warm pyrolyzedsolids in the presence of the air.

Following cooling to ambient conditions, the carbonaceous solids may berecovered and stored, conveyed to another site operation, transported toanother site, or otherwise disposed, traded, or sold. The solids may befed to a unit to reduce particle size. A variety of size-reduction unitsare known in the art, including crushers, shredders, grinders,pulverizers, jet mills, pin mills, and ball mills.

Screening or some other means for separation based on particle size maybe included. The screening may be upstream or downstream of grinding, ifpresent. A portion of the screened material (e.g., large chunks) may bereturned to the grinding unit. The small and large particles may berecovered for separate downstream uses. In some embodiments, cooledpyrolyzed solids are ground into a fine powder, such as a pulverizedcarbon or activated carbon product or increased strength.

Various additives may be introduced throughout the process, before,during, or after any step disclosed herein. The additives may be broadlyclassified as process additives, selected to improve process performancesuch as carbon yield or pyrolysis time/temperature to achieve a desiredcarbon purity; and product additives, selected to improve one or moreproperties of the high-carbon biogenic reagent, or a downstream productincorporating the reagent. Certain additives may provide enhancedprocess and product characteristics, such as overall yield of biogenicreagent compared to the amount of biomass feedstock.

Additives may be added before, during, or after any one or more steps ofthe process, including into the feedstock itself at any time, before orafter it is harvested. Additive treatment may be incorporated prior to,during, or after feedstock sizing, drying, or other preparation.Additives may be incorporated at or on feedstock supply facilities,transport trucks, unloading equipment, storage bins, conveyors(including open or closed conveyors), dryers, process heaters, or anyother units. Additives may be added anywhere into the pyrolysis processitself, using suitable means for introducing additives. Additives may beadded after carbonization, or even after pulverization, if desired.

In some embodiments, an additive is selected from a metal, a metaloxide, a metal hydroxide, or a combination thereof. For example anadditive may be selected from, but is by no means limited to, magnesium,manganese, aluminum, nickel, chromium, silicon, boron, cerium,molybdenum, phosphorus, tungsten, vanadium, iron halide, iron chloride,iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorite,fluorospar, bentonite, calcium oxide, lime, and combinations thereof.

In some embodiments, an additive is selected from an acid, a base, or asalt thereof. For example an additive may be selected from, but is by nomeans limited to, sodium hydroxide, potassium hydroxide, magnesiumoxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassiumpermanganate, or combinations thereof.

In some embodiments, an additive is selected from a metal halide. Metalhalides are compounds between metals and halogens (fluorine, chlorine,bromine, iodine, and astatine). The halogens can form many compoundswith metals. Metal halides are generally obtained by direct combination,or more commonly, neutralization of basic metal salt with a hydrohalicacid. In some embodiments, an additive is selected from iron halide(FeX₂ and/or FeX₃), iron chloride (FeCl₂ and/or FeCl₃), iron bromide(FeBr₂ and/or FeBr₃), or hydrates thereof, and any combinations thereof.

Additives may result in a final product with higher energy content(energy density). An increase in energy content may result from anincrease in total carbon, fixed carbon, volatile carbon, or evenhydrogen. Alternatively or additionally, the increase in energy contentmay result from removal of non-combustible matter or of material havinglower energy density than carbon. In some embodiments, additives reducethe extent of liquid formation, in favor of solid and gas formation, orin favor of solid formation.

In various embodiments, additives chemically modify the startingbiomass, or the treated biomass prior to pyrolysis, to reduce rupture ofcell walls for greater strength/integrity. In some embodiments,additives may increase fixed carbon content of biomass feedstock priorto pyrolysis.

Additives may result in a final biogenic reagent with improvedmechanical properties, such as yield strength, compressive strength,tensile strength, fatigue strength, impact strength, elastic modulus,bulk modulus, or shear modulus. Additives may improve mechanicalproperties by simply being present (e.g., the additive itself impartsstrength to the mixture) or due to some transformation that takes placewithin the additive phase or within the resulting mixture. For example,reactions such as vitrification may occur within a portion of thebiogenic reagent that includes the additive, thereby improving the finalstrength.

Chemical additives may be applied to wet or dry biomass feedstocks. Theadditives may be applied as a solid powder, a spray, a mist, a liquid,or a vapor. In some embodiments, additives may be introduced throughspraying of a liquid solution (such as an aqueous solution or in asolvent), or by soaking in tanks, bins, bags, or other containers.

In certain embodiments, dip pretreatment is employed wherein the solidfeedstock is dipped into a bath comprising the additive, eitherbatchwise or continuously, for a time sufficient to allow penetration ofthe additive into the solid feed material.

In some embodiments, additives applied to the feedstock may reduceenergy requirements for the pyrolysis, and/or increase the yield of thecarbonaceous product. In these or other embodiments, additives appliedto the feedstock may provide functionality that is desired for theintended use of the carbonaceous product, as will be further describedbelow regarding compositions.

The throughput, or process capacity, may vary widely from smalllaboratory-scale units to full commercial-scale biorefineries, includingany pilot, demonstration, or semi-commercial scale. In variousembodiments, the process capacity is at least about 1 kg/day, 10 kg/day,100 kg/day, 1 ton/day (all tons are metric tons), 10 tons/day, 100tons/day, 500 tons/day, 1000 tons/day, 2000 tons/day, or higher.

In some embodiments, a portion of solids produced may be recycled to thefront end of the process, i.e. to the drying or deaeration unit ordirectly to the BPU or reactor. By returning to the front end andpassing through the process again, treated solids may become higher infixed carbon. Solid, liquid, and gas streams produced or existing withinthe process can be independently recycled, passed to subsequent steps,or removed/purged from the process at any point.

In some embodiments, pyrolyzed material is recovered and then fed to aseparate reactor for further pyrolysis, to create a product with highercarbon purity. In some embodiments, the secondary process may beconducted in a simple container, such as a steel drum, in which heatedinert gas (such as heated N₂) is passed through. Other containers usefulfor this purpose include process tanks, barrels, bins, totes, sacks, androll-offs. This secondary sweep gas with volatiles may be sent to theprocess gas heater, or back to the main BPU, for example. To cool thefinal product, another stream of inert gas, which is initially atambient temperature for example, may be passed through the solids tocool the solids, and then returned to an inert gas preheat system. Invarious embodiments, the secondary process takes place in a separatecarbonization or pyrolysis reactor, in which preheated substantiallyinert gas is inputted to pyrolyze the material and drive carbonization.

Some variations of the invention provide a high-carbon biogenic reagentproduction system comprising:

(a) a material feed system configured to introduce a carbon-containingfeedstock;

(b) an optional dryer, disposed in operable communication with thematerial feed system, configured to remove moisture contained within acarbon-containing feedstock;

(c) a biomass processing unit including a plurality of zones, disposedin operable communication with the dryer, wherein the biomass processingunit contains at least a pyrolysis zone disposed in operablecommunication with a spatially separated cooling zone, and wherein thebiomass processing unit is configured with an outlet to removecondensable vapors and non-condensable gases from solids;

(d) an external cooler, disposed in operable communication with thebiomass processing unit; and

(e) a carbon recovery unit, disposed in operable communication with thecooler.

Some variations provide a high-carbon biogenic reagent production systemcomprising:

(a) a material feed system configured to introduce a carbon-containingfeedstock;

(b) an optional dryer, disposed in operable communication with thematerial feed system, configured to remove moisture contained within acarbon-containing feedstock;

(c) an optional preheater, disposed in operable communication with thedryer, configured to heat and/or mildly pyrolyze the feedstock;

(d) a pyrolysis reactor, disposed in operable communication with thepreheater, configured to pyrolyze the feedstock;

(e) a cooler, disposed in operable communication with the pyrolysisreactor, configured to cool pyrolyzed solids; and

(f) a carbon recovery unit, disposed in operable communication with thecooler, wherein the system is configured with at least one gas outlet toremove condensable vapors and non-condensable gases from solids.

The material feed system may be physically integrated with the BPU, suchas through the use of a screw material feed system or auger mechanism tointroduce feed solids into one of the reactors or zones.

In some embodiments, the system further comprises a preheating zone,disposed in operable communication with the pyrolysis zone. Each of thepyrolysis zone, cooling zone, and preheating zone (it present) may belocated within a single BPU, or may be located in separate BPUs.

Optionally, the dryer may be configured as a drying zone within the BPU.Optionally, the cooler may be disposed within the BPU (i.e., configuredas an additional cooling zone or integrated with the cooling zonediscussed above).

The system may include a purging means for removing oxygen from thesystem. For example, the purging means may comprise one or more inletsto introduce a substantially inert gas, and one or more outlets toremove the substantially inert gas and displaced oxygen from the system.In some embodiments, the purging means is a deaerater disposed inoperable communication between the dryer and the BPU.

The BPU can be configured with at least a first gas inlet and a firstgas outlet. The first gas inlet and the first gas outlet may be disposedin communication with different zones, or with the same zones.

In some embodiments, the BPU is configured with a second gas inletand/or a second gas outlet. In some embodiments, the BPU is configuredwith a third gas inlet and/or a third gas outlet. In some embodiments,the BPU is configured with a fourth gas inlet and/or a fourth gasoutlet. In some embodiments, each zone present in the BPU is configuredwith a gas inlet and a gas outlet.

Gas inlets and outlets allow not only introduction and withdrawal ofvapor, but gas outlets (probes) in particular allow precise processmonitoring and control across various stages of the process, up to andpotentially including all stages of the process. Precise processmonitoring would be expected to result in yield and efficiencyimprovements, both dynamically as well as over a period of time whenoperational history can be utilized to adjust process conditions.

In some embodiments (see, generally, FIG. 4), a reaction gas probe isdisposed in operable communication with the pyrolysis zone. Such areaction gas probe may be useful to extract gases and analyze them, inorder to determine extent of reaction, pyrolysis selectivity, or otherprocess monitoring. Then, based on the measurement, the process may becontrolled or adjusted in any number of ways, such as by adjusting feedrate, rate of inert gas sweep, temperature (of one or more zones),pressure (of one or more zones), additives, and so on.

As intended herein, “monitor and control” via reaction gas probes shouldbe construed to include any one or more sample extractions via reactiongas probes, and optionally making process or equipment adjustments basedon the measurements, if deemed necessary or desirable, using well-knownprinciples of process control (feedback, feedforward,proportional-integral-derivative logic, etc.).

A reaction gas probe may be configured to extract gas samples in anumber of ways. For example, a sampling line may have a lower pressurethan the pyrolysis reactor pressure, so that when the sampling line isopened an amount of gas can readily be extracted from pyrolysis zone.The sampling line may be under vacuum, such as when the pyrolysis zoneis near atmospheric pressure. Typically, a reaction gas probe will beassociated with one gas output, or a portion thereof (e.g., a line splitfrom a gas output line).

In some embodiments, both a gas input and a gas output are utilized as areaction gas probe by periodically introducing an inert gas into a zone,and pulling the inert gas with a process sample out of the gas output(“sample sweep”). Such an arrangement could be used in a zone that doesnot otherwise have a gas inlet/outlet for the substantially inert gasfor processing, or, the reaction gas probe could be associated with aseparate gas inlet/outlet that is in addition to process inlets andoutlets. A sampling inert gas that is introduced and extractedperiodically for sampling (in embodiments that utilize sample sweeps)could even be different than the process inert gas, if desired, eitherfor reasons of accuracy in analysis or to introduce an analyticaltracer.

For example, acetic acid concentration in the gas phase of the pyrolysiszone may be measured using a gas probe to extract a sample, which isthen analyzed using a suitable technique (such as gas chromatography,GC; mass spectroscopy, MS; GC-MS, or Fourier-Transform InfraredSpectroscopy, FTIR). CO and/or CO₂ concentration in the gas phase couldbe measured and used as an indication of the pyrolysis selectivitytoward gases/vapors, for example. Terpene concentration in the gas phasecould be measured and used as an indication of the pyrolysis selectivitytoward liquids, and so on.

In some embodiments, the system further comprises at least oneadditional gas probe disposed in operable communication with the coolingzone, or with the drying zone (if present) or the preheating zone (ifpresent).

A gas probe for the cooling zone could be useful to determine the extentof any additional chemistry taking place in the cooling zone, forexample. A gas probe in the cooling zone could also be useful as anindependent measurement of temperature (in addition, for example, to athermocouple disposed in the cooling zone). This independent measurementmay be a correlation of cooling temperature with a measured amount of acertain species. The correlation could be separately developed, or couldbe established after some period of process operation.

A gas probe for the drying zone could be useful to determine the extentof drying, by measuring water content, for example. A gas probe in thepreheating zone could be useful to determine the extent of any mildpyrolysis taking place, for example.

In certain embodiments, the cooling zone is configured with a gas inlet,and the pyrolysis zone is configured with a gas outlet, to generatesubstantially countercurrent flow of the gas phase relative to the solidphase. Alternatively, or additionally, the preheating zone (when it ispresent) may be configured with a gas outlet, to generate substantiallycountercurrent flow of the gas phase relative to the solid phase.Alternatively, or additionally, the drying zone may be configured with agas outlet, to generate substantially countercurrent flow.

The pyrolysis reactor or reactors may be selected from any suitablereactor configuration that is capable of carrying out the pyrolysisprocess. Exemplary reactor configurations include, but are not limitedto, fixed-bed reactors, fluidized-bed reactors, entrained-flow reactors,augers, rotating cones, rotary drum kilns, calciners, roasters,moving-bed reactors, transport-bed reactors, ablative reactors, rotatingcones, or microwave-assisted pyrolysis reactors.

In some embodiments in which an auger is used, sand or another heatcarrier can optionally be employed. For example, the feedstock and sandcan be fed at one end of a screw. The screw mixes the sand and feedstockand conveys them through the reactor. The screw can provide good controlof the feedstock residence time and does not dilute the pyrolyzedproducts with a carrier or fluidizing gas. The sand can be reheated in aseparate vessel.

In some embodiments in which an ablative process is used, the feedstockis moved at a high speed against a hot metal surface. Ablation of anychar forming at surfaces can maintain a high rate of heat transfer. Suchapparatus can prevent dilution of products. As an alternative, thefeedstock particles may be suspended in a carrier gas and introduced ata high speed through a cyclone whose wall is heated.

In some embodiments in which a fluidized-bed reactor is used, thefeedstock can be introduced into a bed of hot sand fluidized by a gas,which is typically a recirculated product gas. Reference herein to“sand” shall also include similar, substantially inert materials, suchas glass particles, recovered ash particles, and the like. Highheat-transfer rates from fluidized sand can result in rapid heating ofthe feedstock. There can be some ablation by attrition with the sandparticles. Heat is usually provided by heat-exchanger tubes throughwhich hot combustion gas flows.

Circulating fluidized-bed reactors can be employed, wherein gas, sand,and feedstock move together. Exemplary transport gases includerecirculated product gases and combustion gases. High heat-transferrates from the sand ensure rapid heating of the feedstock, and ablationis expected to be stronger than with regular fluidized beds. A separatorcan be employed to separate the product gases from the sand and charparticles. The sand particles can be reheated in a fluidized burnervessel and recycled to the reactor.

In some embodiments, the BPU is a continuous reactor comprising afeedstock inlet, a plurality of spatially separated zones configured forseparately controlling the temperature and mixing within each of thezones, and a carbonaceous-solids outlet, wherein one of the zones isconfigured with a first gas inlet for introducing a substantially inertgas into the BPU, and wherein one of the zones is configured with afirst gas outlet.

In various embodiments the reactor includes at least two, three, four,or more zones. Each of the zones is disposed in communication withseparately adjustable heating means independently selected from thegroup consisting of electrical heat transfer, steam heat transfer,hot-oil heat transfer, phase-change heat transfer, waste heat transfer,and combinations thereof. In some embodiments, at least one zone isheated with an effluent stream from the process gas heater, if present.

The BPU may be configured for separately adjusting gas-phase compositionand gas-phase residence time of at least two zones, up to and includingall zones present in the BPU.

The BPU may be equipped with a second gas inlet and/or a second gasoutlet. In some embodiments, the BPU is configured with a gas inlet ineach zone. In these or other embodiments, the BPU is configured with agas outlet in each zone. The BPU may be a cocurrent or countercurrentreactor.

In some embodiments, the material feed system comprises a screw or augerfeed mechanism. In some embodiments, the carbonaceous-solids outletcomprises a screw or auger output mechanism.

Certain embodiments utilize a rotating calciner with a screw materialfeed system. In these embodiments, some or all of the BPU is axiallyrotatable, i.e. it spins about its centerline axis. The speed ofrotation will impact the solid flow pattern, and heat and masstransport. Each of the zones may be configured with flights disposed oninternal walls, to provide agitation of solids. The flights may beseparately adjustable in each of the zones.

Other means of agitating solids may be employed, such as augers, screws,or paddle conveyors. In some embodiments, the BPU includes a single,continuous auger disposed throughout each of the zones. In otherembodiments, the reactor includes twin screws disposed throughout eachof the zones.

Some systems are designed specifically with the capability to maintainthe approximate size of feed material throughout the process—that is, toprocess the biomass feedstock without destroying or significantlydamaging its structure. In some embodiments, the pyrolysis zone does notcontain augers, screws, or rakes that would tend to greatly reduce thesize of feed material being pyrolyzed.

In some embodiments of the invention, the system further includes aprocess gas heater disposed in operable communication with the outlet atwhich condensable vapors and non-condensable gases are removed. Theprocess gas heater can be configured to receive a separate fuel (such asnatural gas) and an oxidant (such as air) into a combustion chamber,adapted for combustion of the fuel and at least a portion of thecondensable vapors. Certain non-condensable gases may also be oxidized,such as CO or CH₄, to CO₂.

When a process gas heater is employed, the system may include a heatexchanger disposed between the process gas heater and the dryer,configured to utilize at least some of the heat of the combustion forthe dryer. This embodiment can contribute significantly to the overallenergy efficiency of the process.

In some embodiments, the system further comprises a material enrichmentunit, disposed in operable communication with the cooler, configured forcombining condensable vapors, in at least partially condensed form, withthe solids. The material enrichment unit may increase the carbon contentof the high-carbon biogenic reagent obtained from the carbon recoveryunit.

The system may further include a separate pyrolysis zone adapted tofurther pyrolyze the high-carbon biogenic reagent to further increaseits carbon content. The separate pyrolysis zone may be a relativelysimply container, unit, or device, such as a tank, barrel, bin, drum,tote, sack, or roll-off.

The overall system may be at a fixed location, or it may be madeportable. The system may be constructed using modules which may besimply duplicated for practical scale-up. The system may also beconstructed using economy-of-scale principles, as is well-known in theprocess industries.

Some variations relating to carbon enrichment of solids will now befurther described. In some embodiments, a process for producing ahigh-carbon biogenic reagent comprises:

(a) providing a carbon-containing feedstock comprising biomass;

(b) optionally drying the feedstock to remove at least a portion ofmoisture contained within the feedstock;

(c) optionally deaerating the feedstock to remove at least a portion ofinterstitial oxygen, if any, contained with the feedstock;

(d) in a pyrolysis zone, pyrolyzing the feedstock in the presence of asubstantially inert gas for at least 10 minutes and with a pyrolysistemperature selected from about 250° C. to about 700° C., to generatehot pyrolyzed solids, condensable vapors, and non-condensable gases;

(e) separating at least a portion of the condensable vapors and at leasta portion of the non-condensable gases from the hot pyrolyzed solids;

(f) in a cooling zone, cooling the hot pyrolyzed solids, in the presenceof the substantially inert gas for at least 5 minutes and with a coolingtemperature less than the pyrolysis temperature, to generate warmpyrolyzed solids;

(g) optionally cooling the warm pyrolyzed solids in a cooler to generatecool pyrolyzed solids;

(h) subsequently passing at least a portion of the condensable vaporsand/or at least a portion of the non-condensable gases from step (e)across the warm pyrolyzed solids and/or the cool pyrolyzed solids, toform enriched pyrolyzed solids with increased carbon content; and

(i) in a carbon recovery unit, recovering a high-carbon biogenic reagentcomprising at least a portion of the enriched pyrolyzed solids.

In some embodiments, step (h) includes passing at least a portion of thecondensable vapors from step (e), in vapor and/or condensed form, acrossthe warm pyrolyzed solids, to produce enriched pyrolyzed solids withincreased carbon content. In some embodiments, step (h) includes passingat least a portion of the non-condensable gases from step (e) across thewarm pyrolyzed solids, to produce enriched pyrolyzed solids withincreased carbon content.

It should be appreciated that in various embodiments, carbon enrichmentincreases carbon content, energy content, as well as mass yield.

Alternatively, or additionally, vapors or gases may be contacted withthe cool pyrolyzed solids. In some embodiments, step (h) includespassing at least a portion of the condensable vapors from step (e), invapor and/or condensed form, across the cool pyrolyzed solids, toproduce enriched pyrolyzed solids with increased carbon content. In someembodiments, step (h) includes passing at least a portion of thenon-condensable gases from step (e) across the cool pyrolyzed solids, toproduce enriched pyrolyzed solids with increased carbon content.

In certain embodiments, step (h) includes passing substantially all ofthe condensable vapors from step (e), in vapor and/or condensed form,across the cool pyrolyzed solids, to produce enriched pyrolyzed solidswith increased carbon content. In certain embodiments, step (h) includespassing substantially all of the non-condensable gases from step (e)across the cool pyrolyzed solids, to produce enriched pyrolyzed solidswith increased carbon content.

The process may include various methods of treating or separating thevapors or gases prior to using them for carbon enrichment. For example,an intermediate feed stream consisting of at least a portion of thecondensable vapors and at least a portion of the non-condensable gases,obtained from step (e), may be fed to a separation unit configured togenerate at least first and second output streams. In certainembodiments, the intermediate feed stream comprises all of thecondensable vapors, all of the non-condensable gases, or both.

Separation techniques can include or use distillation columns, flashvessels, centrifuges, cyclones, membranes, filters, packed beds,capillary columns, and so on. Separation can be principally based, forexample, on distillation, absorption, adsorption, or diffusion, and canutilize differences in vapor pressure, activity, molecular weight,density, viscosity, polarity, chemical functionality, affinity to astationary phase, and any combinations thereof.

In some embodiments, the first and second output streams are separatedfrom the intermediate feed stream based on relative volatility. Forexample, the separation unit may be a distillation column, a flash tank,or a condenser.

Thus in some embodiments, the first output stream comprises thecondensable vapors, and the second output stream comprises thenon-condensable gases. The condensable vapors may include at least onecarbon-containing compound selected from terpenes, alcohols, acids,aldehydes, or ketones. The vapors from pyrolysis may include aromaticcompounds such as benzene, toluene, ethylbenzene, and xylenes. Heavieraromatic compounds, such as refractory tars, may be present in thevapor. The non-condensable gases may include at least onecarbon-containing molecule selected from the group consisting of carbonmonoxide, carbon dioxide, and methane.

In some embodiments, the first and second output streams are separatedintermediate feed stream based on relative polarity. For example, theseparation unit may be a stripping column, a packed bed, achromatography column, or membranes.

Thus in some embodiments, the first output stream comprises polarcompounds, and the second output stream comprises non-polar compounds.The polar compounds may include at least one carbon-containing moleculeselected from the group consisting of methanol, furfural, and aceticacid. The non-polar compounds may include at least one carbon-containingmolecule selected from the group consisting of carbon monoxide, carbondioxide, methane, a terpene, and a terpene derivative.

Step (h) may increase the total carbon content of the high-carbonbiogenic reagent, relative to an otherwise-identical process withoutstep (h). The extent of increase in carbon content may be, for example,about 1%, 2%, 5%, 10%, 15%, 25%, or even higher, in various embodiments.

In some embodiments, step (h) increases the fixed carbon content of thehigh-carbon biogenic reagent. In these or other embodiments, step (h)increases the volatile carbon content of the high-carbon biogenicreagent. Volatile carbon content is the carbon attributed to volatilematter in the reagent. The volatile matter may be, but is not limitedto, hydrocarbons including aliphatic or aromatic compounds (e.g.,terpenes); oxygenates including alcohols, aldehydes, or ketones; andvarious tars. Volatile carbon will typically remain bound or adsorbed tothe solids at ambient conditions but upon heating, will be releasedbefore the fixed carbon would be oxidized, gasified, or otherwisereleased as a vapor.

Depending on conditions associated with step (h), it is possible forsome amount of volatile carbon to become fixed carbon (e.g., viaBoudouard carbon formation from CO). Typically, the volatile matter willbe expected to enter the micropores of the fixed carbon and will bepresent as condensed/adsorbed species, but still relatively volatile.This residual volatility can be more advantageous for fuel applications,compared to product applications requiring high surface area andporosity.

Step (h) may increase the energy content (i.e., energy density) of thehigh-carbon biogenic reagent. The increase in energy content may resultfrom an increase in total carbon, fixed carbon, volatile carbon, or evenhydrogen. The extent of increase in energy content may be, for example,about 1%, 2%, 5%, 10%, 15%, 25%, or even higher, in various embodiments.

Further separations may be employed to recover one or morenon-condensable gases or condensable vapors, for use within the processor further processing. For example, further processing may be includedto produce refined CO or syngas.

As another example, separation of acetic acid may be conducted, followedby reduction of the acetic acid into ethanol. The reduction of theacetic acid may be accomplished, at least in part, using hydrogenderived from the non-condensable gases produced.

Condensable vapors may be used for either energy in the process (such asby thermal oxidation) or in carbon enrichment, to increase the carboncontent of the high-carbon biogenic reagent. Certain non-condensablegases, such as CO or CH₄, may be utilized either for energy in theprocess, or as part of the substantially inert gas for the pyrolysisstep. Combinations of any of the foregoing are also possible.

A potential benefit of including step (h) is that the gas stream isscrubbed, with the resulting gas stream being enriched in CO and CO₂.The resulting gas stream may be utilized for energy recovery, recycledfor carbon enrichment of solids, and/or used as an inert gas in thereactor. Similarly, by separating non-condensable gases from condensablevapors, the CO/CO₂ stream is prepared for use as the inert gas in thereactor system or in the cooling system, for example.

Other variations of the invention are premised on the realization thatthe principles of the carbon-enrichment step may be applied to anyfeedstock in which it is desired to add carbon.

In some embodiments, a batch or continuous process for producing ahigh-carbon biogenic reagent comprises:

(a) providing a solid stream comprising a carbon-containing material;

(b) providing a gas stream comprising condensable carbon-containingvapors, non-condensable carbon-containing gases, or a mixture ofcondensable carbon-containing vapors and non-condensablecarbon-containing gases; and

(c) passing the gas stream across the solid stream under suitableconditions to form a carbon-containing product with increased carboncontent relative to the carbon-containing material.

In some embodiments, the starting carbon-containing material ispyrolyzed biomass or torrefied biomass. The gas stream may be obtainedduring an integrated process that provides the carbon-containingmaterial. Or, the gas stream may be obtained from separate processing ofthe carbon-containing material. The gas stream, or a portion thereof,may be obtained from an external source (e.g., an oven at a lumbermill). Mixtures of gas streams, as well as mixtures of carbon-containingmaterials, from a variety of sources, are possible.

In some embodiments, the process further comprises recycling or reusingthe gas stream for repeating the process to further increase carbonand/or energy content of the carbon-containing product. In someembodiments, the process further comprises recycling or reusing the gasstream for carrying out the process to increase carbon and/or energycontent of another feedstock different from the carbon-containingmaterial.

In some embodiments, the process further includes introducing the gasstream to a separation unit configured to generate at least first andsecond output streams, wherein the gas stream comprises a mixture ofcondensable carbon-containing vapors and non-condensablecarbon-containing gases. The first and second output streams may beseparated based on relative volatility, relative polarity, or any otherproperty. The gas stream may be obtained from separate processing of thecarbon-containing material.

In some embodiments, the process further comprises recycling or reusingthe gas stream for repeating the process to further increase carboncontent of the carbon-containing product. In some embodiments, theprocess further comprises recycling or reusing the gas stream forcarrying out the process to increase carbon content of anotherfeedstock.

The carbon-containing product may have an increased total carboncontent, a higher fixed carbon content, a higher volatile carboncontent, a higher energy content, or any combination thereof, relativeto the starting carbon-containing material.

In related variations, a high-carbon biogenic reagent production systemcomprises:

(a) a material feed system configured to introduce a carbon-containingfeedstock;

(b) an optional dryer, disposed in operable communication with thematerial feed system, configured to remove moisture contained within acarbon-containing feedstock;

(c) a BPU, disposed in operable communication with the dryer, whereinthe BPU contains at least a pyrolysis zone disposed in operablecommunication with a spatially separated cooling zone, and wherein theBPU is configured with an outlet to remove condensable vapors andnon-condensable gases from solids;

(d) a cooler, disposed in operable communication with the BPU;

(e) a material enrichment unit, disposed in operable communication withthe cooler, configured to pass the condensable vapors and/or thenon-condensable gases across the solids, to form enriched solids withincreased carbon content; and

(f) a carbon recovery unit, disposed in operable communication with thematerial enrichment unit.

The system may further comprise a preheating zone, disposed in operablecommunication with the pyrolysis zone. In some embodiments, the dryer isconfigured as a drying zone within the BPU. Each of the zones may belocated within a single BPU or in separate BPUs. Also, the cooler may bedisposed within the BPU.

In some embodiments, the cooling zone is configured with a gas inlet,and the pyrolysis zone is configured with a gas outlet, to generatesubstantially countercurrent flow of the gas phase relative to the solidphase. In these or other embodiments, the preheating zone and/or thedrying zone (or dryer) is configured with a gas outlet, to generatesubstantially countercurrent flow of the gas phase relative to the solidphase.

In particular embodiments, the system incorporates a material enrichmentunit that comprises:

(i) a housing with an upper portion and a lower portion;

(ii) an inlet at a bottom of the lower portion of the housing configuredto carry the condensable vapors and non-condensable gases;

(iii) an outlet at a top of the upper portion of the housing configuredto carry a concentrated gas stream derived from the condensable vaporsand non-condensable gases;

(iv) a path defined between the upper portion and the lower portion ofthe housing; and

(v) a material transport system following the path, the materialtransport system configured to transport the solids, wherein the housingis shaped such that the solids adsorb at least some of the condensablevapors and/or at least some of the non-condensable gases.

The present invention is capable of producing a variety of compositionsuseful as high-carbon biogenic reagents, and products incorporatingthese reagents. In some variations, a high-carbon biogenic reagent isproduced by any process disclosed herein, such as a process comprisingthe steps of:

(a) providing a carbon-containing feedstock comprising biomass;

(b) optionally drying the feedstock to remove at least a portion ofmoisture contained within the feedstock;

(c) optionally deaerating the feedstock to remove at least a portion ofinterstitial oxygen, if any, contained with the feedstock;

(d) in a pyrolysis zone, pyrolyzing the feedstock in the presence of asubstantially inert gas for at least 10 minutes and with a pyrolysistemperature selected from about 250° C. to about 700° C., to generatehot pyrolyzed solids, condensable vapors, and non-condensable gases;

(e) separating at least a portion of the condensable vapors and at leasta portion of the non-condensable gases from the hot pyrolyzed solids;

(f) in a cooling zone, cooling the hot pyrolyzed solids, in the presenceof the substantially inert gas for at least 5 minutes and with a coolingtemperature less than the pyrolysis temperature, to generate warmpyrolyzed solids;

(g) cooling the warm pyrolyzed solids to generate cool pyrolyzed solids;and

(h) recovering a high-carbon biogenic reagent comprising at least aportion of the cool pyrolyzed solids.

In some embodiments, the reagent comprises at least about 55 wt. %, forexample at least 55 wt. %, at least 60 wt. %, at least 65 wt. %, atleast 70 wt %, at least 75 wt. %, at least 80 wt %, at least 85 wt. %,at least 90 wt %, or at least 95 wt % total carbon on a dry basis. Thetotal carbon includes at least fixed carbon, and may further includecarbon from volatile matter. In some embodiments, carbon from volatilematter is about at least 5%, at least 10%, at least 25%, or at least 50%of the total carbon present in the high-carbon biogenic reagent. Fixedcarbon may be measured using ASTM D3172, while volatile carbon may beestimated using ASTM D3175, for example.

The high-carbon biogenic reagent may comprise about 10 wt % or less,such as about 5 wt % or less, hydrogen on a dry basis. The biogenicreagent may comprise about 1 wt % or less, such as about 0.5 wt % orless, nitrogen on a dry basis. The biogenic reagent may comprise about0.5 wt % or less, such as about 0.2 wt % or less, phosphorus on a drybasis. The biogenic reagent may comprise about 0.2 wt % or less, such asabout 0.1 wt % or less, sulfur on a dry basis.

Carbon, hydrogen, and nitrogen may be measured using ASTM D5373 forultimate analysis, for example. Oxygen may be estimated using ASTMD3176, for example. Sulfur may be measured using ASTM D3177, forexample.

Certain embodiments provide reagents with little or essentially nohydrogen (except from any moisture that may be present), nitrogen,phosphorus, or sulfur, and are substantially carbon plus any ash andmoisture present. Therefore, some embodiments provide a material with upto and including 100% carbon, on a dry/ash-free (DAF) basis.

Generally speaking, feedstocks such as biomass contain non-volatilespecies, including silica and various metals, which are not readilyreleased during pyrolysis. It is of course possible to utilize ash-freefeedstocks, in which case there should not be substantial quantities ofash in the pyrolyzed solids. Ash may be measured using ASTM D3174, forexample.

Various amounts of non-combustible matter, such as ash, may be present.The high-carbon biogenic reagent may comprise about 10 wt % or less,such as about 5 wt %, about 2 wt %, about 1 wt % or less non-combustiblematter on a dry basis. In certain embodiments, the reagent containslittle ash, or even essentially no ash or other non-combustible matter.Therefore, some embodiments provide essentially pure carbon, including100% carbon, on a dry basis.

Various amounts of moisture may be present. On a total mass basis, thehigh-carbon biogenic reagent may comprise at least 1 wt %, 2 wt %, 5 wt%, 10 wt %, 15 wt %, 25 wt %, 35 wt %, 50 wt %, or more moisture. Asintended herein, “moisture” is to be construed as including any form ofwater present in the biogenic reagent, including absorbed moisture,adsorbed water molecules, chemical hydrates, and physical hydrates. Theequilibrium moisture content may vary at least with the localenvironment, such as the relative humidity. Also, moisture may varyduring transportation, preparation for use, and other logistics.Moisture may be measured using ASTM D3173, for example.

The high-carbon biogenic reagent may have various “energy content” whichfor present purposes means the energy density based on the higherheating value associated with total combustion of the bone-dry reagent.For example, the high-carbon biogenic reagent may possess an energycontent of about at least 11,000 Btu/lb, at least 12,000 Btu/lb, atleast 13,000 Btu/lb, at least 14,000 Btu/lb, or at least 15,000 Btu/lb.In certain embodiments, the energy content is between about14,000-15,000 Btu/lb. The energy content may be measured using ASTMD5865, for example.

The high-carbon biogenic reagent may be formed into a powder, such as acoarse powder or a fine powder. For example, the reagent may be formedinto a powder with an average mesh size of about 200 mesh, about 100mesh, about 50 mesh, about 10 mesh, about 6 mesh, about 4 mesh, or about2 mesh, in embodiments.

In some embodiments, the high-carbon biogenic reagent is formed intostructural objects comprising pressed, binded, or agglomeratedparticles. The starting material to form these objects may be a powderform of the reagent, such as an intermediate obtained by particle-sizereduction. The objects may be formed by mechanical pressing or otherforces, optionally with a binder or other means of agglomeratingparticles together.

In some embodiments, the high-carbon biogenic reagent is produced in theform of structural objects whose structure substantially derives fromthe feedstock. For example, feedstock chips may produce product chips ofhigh-carbon biogenic reagent. Or, feedstock cylinders may producehigh-carbon biogenic reagent cylinders, which may be somewhat smallerbut otherwise maintain the basic structure and geometry of the startingmaterial.

A high-carbon biogenic reagent according to the present invention may beproduced as, or formed into, an object that has a minimum dimension ofat least about 1 cm, 2 cm, 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm, 10cm, or higher. In various embodiments, the minimum dimension or maximumdimension can be a length, width, or diameter.

Other variations of the invention relate to the incorporation ofadditives into the process, into the product, or both. In someembodiments, the high-carbon biogenic reagent includes at least oneprocess additive incorporated during the process. In these or otherembodiments, the reagent includes at least one product additiveintroduced to the reagent following the process.

In some embodiments, a high-carbon biogenic reagent comprises, on a drybasis:

55 wt % or more total carbon;

5 wt % or less hydrogen;

1 wt % or less nitrogen;

0.5 wt % or less phosphorus;

0.2 wt % or less sulfur; and

an additive selected from a metal, a metal oxide, a metal hydroxide, ametal halide, or a combination thereof.

The additive may be selected from, but is by no means limited to,magnesium, manganese, aluminum, nickel, chromium, silicon, boron,cerium, molybdenum, phosphorus, tungsten, vanadium, iron halide, ironchloride, iron bromide, magnesium oxide, dolomite, dolomitic lime,fluorite, fluorospar, bentonite, calcium oxide, lime, and combinationsthereof.

In some embodiments, a high-carbon biogenic reagent comprising, on a drybasis:

55 wt % or more total carbon;

5 wt % or less hydrogen;

1 wt % or less nitrogen;

0.5 wt % or less phosphorus;

0.2 wt % or less sulfur; and

an additive selected from an acid, a base, or a salt thereof.

The additive may be selected from, but is by no means limited to, sodiumhydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide,hydrogen chloride, sodium silicate, potassium permanganate, orcombinations thereof.

In certain embodiments, a high-carbon biogenic reagent comprises, on adry basis:

55 wt % or more total carbon;

5 wt % or less hydrogen;

1 wt % or less nitrogen;

0.5 wt % or less phosphorus;

0.2 wt % or less sulfur;

a first additive selected from a metal, metal oxide, metal hydroxide, ametal halide, or a combination thereof; and

a second additive selected from an acid, a base, or a salt thereof,

wherein the first additive is different from the second additive.

The first additive may be selected from magnesium, manganese, aluminum,nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus,tungsten, vanadium, iron halide, iron chloride, iron bromide, magnesiumoxide, dolomite, dolomitic lime, fluorite, fluorospar, bentonite,calcium oxide, lime, and combinations thereof, while the second additivemay be independently selected from sodium hydroxide, potassiumhydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodiumsilicate, potassium permanganate, or combinations thereof.

A certain high-carbon biogenic reagent consists essentially of, on a drybasis, carbon, hydrogen, nitrogen, phosphorus, sulfur, non-combustiblematter, and an additive selected from the group consisting of magnesium,manganese, aluminum, nickel, chromium, silicon, boron, cerium,molybdenum, phosphorus, tungsten, vanadium, iron halide, iron chloride,iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorite,fluorospar, bentonite, calcium oxide, lime, and combinations thereof.

A certain high-carbon biogenic reagent consists essentially of, on a drybasis, carbon, hydrogen, nitrogen, phosphorus, sulfur, non-combustiblematter, and an additive selected from the group consisting of sodiumhydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide,hydrogen chloride, sodium silicate, and combinations thereof.

The amount of additive (or total additives) may vary widely, such asfrom about 0.01 wt % to about 25 wt %, including about 0.1 wt %, about 1wt %, about 5 wt %, about 10 wt %, or about 20 wt %. It will beappreciated then when relatively large amounts of additives areincorporated, such as higher than about 1 wt %, there will be areduction in energy content calculated on the basis of the total reagentweight (inclusive of additives). Still, in various embodiments, thehigh-carbon biogenic reagent with additive(s) may possess an energycontent of about at least 11,000 Btu/lb, at least 12,000 Btu/lb, atleast 13,000 Btu/lb, at least 14,000 Btu/lb, or at least 15,000 Btu/lb.

The above discussion regarding product form applies also to embodimentsthat incorporate additives. In fact, certain embodiments incorporateadditives as binders or other modifiers to enrich final properties for aparticular application.

In some embodiments, the majority of carbon contained in the high-carbonbiogenic reagent is classified as renewable carbon. In some embodiments,substantially all of the carbon is classified as renewable carbon. Theremay be certain market mechanisms (e.g., Renewable IdentificationNumbers, tax credits, etc.) wherein value is attributed to the renewablecarbon content within the high-carbon biogenic reagent.

In certain embodiments, the fixed carbon may be classified asnon-renewable carbon (e.g., from coal) while the volatile carbon, whichmay be added separately, may be renewable carbon to increase not onlyenergy content but also renewable carbon value.

The high-carbon biogenic reagents produced as described herein as usefulfor a wide variety of carbonaceous products. The high-carbon biogenicreagent may be a desirable market product itself. High-carbon biogenicreagents as provided herein are associated with lower levels ofimpurities, reduced process emissions, and improved sustainability(including higher renewable carbon content) compared to the state of theart.

In variations, a product includes any of the high-carbon biogenicreagents that may be obtained by the disclosed processes, or that aredescribed in the compositions set forth herein, or any portions,combinations, or derivatives thereof.

Generally speaking, the high-carbon biogenic reagents may be combustedto produce energy (including electricity and heat); partially oxidizedor steam-reformed to produce syngas; utilized for their adsorptive orabsorptive properties; utilized for their reactive properties duringmetal refining (such as reduction of metal oxides) or other industrialprocessing; or utilized for their material properties in carbon steeland various other metal alloys. Essentially, the high-carbon biogenicreagents may be utilized for any market application of carbon-basedcommodities or advanced materials, including specialty uses to bedeveloped.

Prior to suitability or actual use in any product applications, thedisclosed high-carbon biogenic reagents may be analyzed, measured, andoptionally modified (such as through additives) in various ways. Someproperties of potential interest, other than chemical composition andenergy content, include density, particle size, surface area,microporosity, absorptivity, adsorptivity, binding capacity, reactivity,desulfurization activity, and basicity, to name a few properties.

Products or materials that may incorporate these high-carbon biogenicreagents include, but are by no means limited to, carbon-based blastfurnace addition products, carbon-based taconite pellet additionproducts, ladle addition carbon-based products, met coke carbon-basedproducts, coal replacement products, carbon-based coking products,carbon breeze products, fluidized-bed carbon-based feedstocks,carbon-based furnace addition products, injectable carbon-basedproducts, pulverized carbon-based products, stoker carbon-basedproducts, carbon electrodes, or activated carbon products.

Use of the disclosed high-carbon biogenic reagents in metals productioncan reduce slag, increase overall efficiency, and reduce lifecycleenvironmental impacts. Therefore, embodiments of this invention areparticularly well-suited for metal processing and manufacturing.

Some variations of the invention utilize the high-carbon biogenicreagents as carbon-based blast furnace addition products. A blastfurnace is a type of metallurgical furnace used for smelting to produceindustrial metals, such as (but not limited to) iron. Smelting is a formof extractive metallurgy; its main use is to produce a metal from itsore. Smelting uses heat and a chemical reducing agent to decompose theore. The carbon and/or the carbon monoxide derived from the carbonremoves oxygen from the ore, leaving behind elemental metal.

The reducing agent may consist of, or comprise, a high-carbon biogenicreagent. In a blast furnace, high-carbon biogenic reagent, ore, andtypically limestone may be continuously supplied through the top of thefurnace, while air (optionally with oxygen enrichment) is blown into thebottom of the chamber, so that the chemical reactions take placethroughout the furnace as the material moves downward. The end productsare usually molten metal and slag phases tapped from the bottom, andflue gases exiting from the top of the furnace. The downward flow of theore in contact with an upflow of hot, carbon monoxide-rich gases is acountercurrent process.

Carbon quality in the blast furnace is measured by its resistance todegradation. The role of the carbon as a permeable medium is crucial ineconomic blast furnace operation. The degradation of the carbon varieswith the position in the blast furnace and involves the combination ofreaction with CO₂, H₂O, or O₂ and the abrasion of carbon particlesagainst each other and other components of the burden. Degraded carbonparticles may cause plugging and poor performance.

The Coke Reactivity test is a highly regarded measure of the performanceof carbon in a blast furnace. This test has two components: the CokeReactivity Index (CRI) and the Coke Strength after Reaction (CSR). Acarbon-based material with a low CRI value (high reactivity) and a highCSR value can provide improved blast furnace performance. CRI can bedetermined according to any suitable method known in the art, forexample by ASTM Method DS341 on an as-received basis.

In some embodiments, the high-carbon biogenic reagent, when blended withanother carbon source, for example up to about 10 wt % or more, providesa final carbon product having suitable properties for combustion in ablast furnace.

The strength of the high-carbon biogenic reagent may be determined byany suitable method known in the art, for example by a drop-shattertest, or a CSR test. In some embodiments, the high-carbon biogenicreagent, when blended with another source of carbon, provides a finalcarbon product having CSR of at least about 50%, 60%, or 70%. Acombination product may also provide a final coke product having asuitable reactivity for combustion in a blast furnace. In someembodiments, the product has a CRI such that the high-carbon biogenicreagent is suitable for use as an additive or replacement for met coal,met coke, coke breeze, foundry coke, or injectable coal.

Some embodiments employ one or more additives in an amount sufficient toprovide a high-carbon biogenic reagent that, when added to anothercarbon source (e.g., coke) having a CRI or CSR insufficient for use as ablast furnace product, provides a composite product with a CRI and/orCSR sufficient for use in a blast furnace. In some embodiments, one ormore additives are present in an amount sufficient to provide ahigh-carbon biogenic reagent having a CRI of not more than about 40%,30%, or 20%.

In some embodiments, one or more additives selected from the alkalineearth metals, or oxides or carbonates thereof, are introduced during orafter the process of producing a high-carbon biogenic reagent. Forexample, calcium, calcium oxide, calcium carbonate, magnesium oxide, ormagnesium carbonate may be introduced as additives. The addition ofthese compounds before, during, or after pyrolysis may increase ordecrease the reactivity of the high-carbon biogenic reagent in a blastfurnace. These compounds may lead to stronger materials, i.e. higherCSR, thereby improving blast-furnace efficiency. In addition, additivessuch as those selected from the alkaline earth metals, or oxides orcarbonates thereof, may lead to lower emissions (e.g., SO₂).

In some embodiments, a high-carbon biogenic reagent contains not only ahigh fixed-carbon content but also a fairly high fraction of volatilecarbon, as described above. The volatile matter may be desirable formetal oxide reduction because it is expected to have better masstransport into the metal oxide at lower temperatures. Compared tofossil-fuel based products such as coke, high-carbon biogenic reagentsmay have sufficient strength and more fixed and volatile carbon, whichleads to greater reactivity.

In some embodiments, a blast furnace replacement product is ahigh-carbon biogenic reagent according to the present inventioncomprising at least about 55 wt % carbon, not more than about 0.5 wt %sulfur, not more than about 8 wt % non-combustible material, and a heatvalue of at least about 11,000 Btu per pound. In some embodiments, theblast furnace replacement product further comprises not more than about0.035 wt % phosphorous, about 0.5 wt % to about 50 wt % volatile matter,and optionally one or more additives. In some embodiments, the blastfurnace replacement product comprises about 2 wt % to about 15 wt %dolomite, about 2 wt % to about 15 wt % dolomitic lime, about 2 wt % toabout 15 wt % bentonite, and/or about 2 wt % to about 15 wt % calciumoxide. In some embodiments, the blast furnace replacement product hasdimensions substantially in the range of about 1 cm to about 10 cm.

In some embodiments, a high-carbon biogenic reagent according to thepresent invention is useful as a foundry coke replacement product.Foundry coke is generally characterized as having a carbon content of atleast about 85 wt %, a sulfur content of about 0.6 wt %, not more thanabout 1.5 wt % volatile matter, not more than about 13 wt % ash, notmore than about 8 wt % moisture, about 0.035 wt % phosphorus, a CRIvalue of about 30, and dimensions ranging from about 5 cm to about 25cm.

Some variations of the invention utilize the high-carbon biogenicreagents as carbon-based taconite pellet addition products. The oresused in making iron and steel are iron oxides. The major iron oxide oresare hematite, limonite (also called brown ore), taconite, and magnetite,a black ore. Taconite is a low-grade but important ore, which containsboth magnetite and hematite. The iron content of taconite is generally25 wt % to 30 wt %. Blast furnaces typically require at least a 50 wt %iron content ore for efficient operation. Iron ores may undergobeneficiation including crushing, screening, tumbling, flotation, andmagnetic separation. The refined ore is enriched to over 60% iron and isoften formed into pellets before shipping.

For example, taconite may be ground into a fine powder and combined witha binder such as bentonite clay and limestone. Pellets about onecentimeter in diameter may be formed, containing approximately 65 wt %iron, for example. The pellets are fired, oxidizing magnetite tohematite. The pellets are durable which ensures that the blast furnacecharge remains porous enough to allow heated gas to pass through andreact with the pelletized ore.

The taconite pellets may be fed to a blast furnace to produce iron, asdescribed above with reference to blast furnace addition products. Insome embodiments, a high-carbon biogenic reagent is introduced to theblast furnace. In these or other embodiments, a high-carbon biogenicreagent is incorporated into the taconite pellet itself. For example,taconite ore powder, after beneficiation, may be mixed with ahigh-carbon biogenic reagent and a binder and rolled into small objects,then baked to hardness. In such embodiments, taconite-carbon pelletswith the appropriate composition may conveniently be introduced into ablast furnace without the need for a separate source of carbon.

Some variations of the invention utilize the high-carbon biogenicreagents as ladle addition carbon-based products. A ladle is a vesselused to transport and pour out molten metals. Casting ladles are used topour molten metal into molds to produce the casting. Transfers ladle areused to transfer a large amount of molten metal from one process toanother. Treatment ladles are used for a process to take place withinthe ladle to change some aspect of the molten metal, such as theconversion of cast iron to ductile iron by the addition of variouselements into the ladle.

High-carbon biogenic reagents may be introduced to any type of ladle,but typically carbon will be added to treatment ladles in suitableamounts based on the target carbon content. Carbon injected into ladlesmay be in the form of fine powder, for good mass transport of the carboninto the final composition. In some embodiments, a high-carbon biogenicreagent according to the present invention, when used as a ladleaddition product, has a minimum dimension of about 0.5 cm, such as about0.75 cm, about 1 cm, about 1.5 cm, or higher.

In some embodiments, a high carbon biogenic reagent according to thepresent invention is useful as a ladle addition carbon additive at, forexample, basic oxygen furnace or electric arc furnace facilitieswherever ladle addition of carbon would be used (e.g., added to ladlecarbon during steel manufacturing). In some embodiments, the ladleaddition carbon additive is a high-carbon biogenic reagent comprising atleast about 55 wt. % carbon, no more than about 0.4 wt. % sulfur, nomore than about 0.035 wt. % phosphorous, and a heat value of at leastabout 11,000 BTU per pound.

In some embodiments, the ladle addition carbon additive additionallycomprises up to about 5 wt % manganese, up to about 5 wt % calciumoxide, and/or up to about 5 wt % dolomitic lime. In some embodiments,the ladle addition carbon additive has a minimum dimension of about ¼inches. In some embodiments, the ladle addition carbon product has amaximum dimension of about ½ inches. In some embodiments, the ladleaddition carbon additive has a minimum dimension of about ¼ inches and amaximum dimension of about ½ inches. In some embodiments, the ladleaddition carbon product is substantially free of fossil fuel.

Direct-reduced iron (DRI), also called sponge iron, is produced fromdirect reduction of iron ore (in the form of lumps, pellets or fines) bya reducing gas produced from natural gas or coal. The reducing gas istypically syngas, a mixture of hydrogen and carbon monoxide which actsas reducing agent. The high-carbon biogenic reagent as provided hereinmay be converted into a gas stream comprising CO, to act as a reducingagent to produce direct-reduced iron.

Iron nuggets are a high-quality steelmaking and iron-casting feedmaterial. Iron nuggets are essentially all iron and carbon, with almostno gangue (slag) and low levels of metal residuals. They are a premiumgrade pig iron product with superior shipping and handlingcharacteristics. The carbon contained in iron nuggets, or any portionthereof, may be the high-carbon biogenic reagent provided herein. Ironnuggets may be produced through the reduction of iron ore in a rotaryhearth furnace, using a high-carbon biogenic reagent as the reductantand energy source.

Some variations of the invention utilize the high-carbon biogenicreagents as metallurgical coke carbon-based products. Metallurgicalcoke, also known as “met” coke, is a carbon material normallymanufactured by the destructive distillation of various blends ofbituminous coal. The final solid is a non-melting carbon calledmetallurgical coke. As a result of the loss of volatile gases and ofpartial melting, met coke has an open, porous morphology. Met coke has avery low volatile content. However, the ash constituents, that were partof the original bituminous coal feedstock, remain encapsulated in theresultant coke. Met coke feedstocks are available in a wide range ofsizes from fine powder to basketball-sized lumps. Typical purities rangefrom 86-92 wt % fixed carbon.

Metallurgical coke is used where a high-quality, tough, resilient,wearing carbon is required. Applications include, but are not limitedto, conductive flooring, friction materials (e.g., carbon linings),foundry coatings, foundry carbon raiser, corrosion materials, drillingapplications, reducing agents, heat-treatment agents, ceramic packingmedia, electrolytic processes, and oxygen exclusion.

Met coke may be characterized as having a heat value of about 10,000 to14,000 Btu per pound and an ash content of about 10 wt % or greater.Thus, in some embodiments, a met coke replacement product comprises ahigh-carbon biogenic reagent according to the present inventioncomprising at least about 80 wt %, 85 wt %, or 90 wt % carbon, not morethan about 0.8 wt % sulfur, not more than about 3 wt % volatile matter,not more than about 15 wt % ash, not more than about 13 wt % moisture,and not more than about 0.035 wt % phosphorus. In some embodiments, themet coke replacement product comprises at least about 55 wt. % carbon,no more than about 0.4 wt. % sulfur, no more than about 0.035 wt. %phosphorous, and a heat value of at least about 11,000 BTU per pound. Insome embodiments, a met coke replacement product further comprises about2 wt. % to about 15 wt. % of dolomite, for example, about 1 wt. %, about3 wt. %, about 4 wt. %, about 5 wt. %, about 6 wt. %, about 7 wt. %,about 8 wt. %, about 9 wt. %, about 10 wt. %, about 11 wt. %, about 12wt. %, about 13 wt. %, about 14 wt. %, or about 15 wt. % of dolomite. Insome embodiments, a met coke replacement product further comprises about2 wt. % to about 15 wt. % of bentonite, for example, about 1 wt. %,about 3 wt. %, about 4 wt. %, about 5 wt. %, about 6 wt. %, about 7 wt.%, about 8 wt. %, about 9 wt. %, about 10 wt. %, about 11 wt. %, about12 wt. %, about 13 wt. %, about 14 wt. %, or about 15 wt. % ofbentonite. In some embodiments, a met coke replacement product furthercomprises about 2 wt. % to about 15 wt. % of calcium oxide, for example,about 1 wt. %, about 3 wt. %, about 4 wt. %, about 5 wt. %, about 6 wt.%, about 7 wt. %, about 8 wt. %, about 9 wt. %, about 10 wt. %, about 11wt. %, about 12 wt. %, about 13 wt. %, about 14 wt. %, or about 15 wt. %of calcium oxide. In some embodiments, a met coke replacement productfurther comprises about 2 wt. % to about 15 wt. % of dolomitic lime, forexample, about 1 wt. %, about 3 wt. %, about 4 wt. %, about 5 wt. %,about 6 wt. %, about 7 wt. %, about 8 wt. %, about 9 wt. %, about 10 wt.%, about 11 wt. %, about 12 wt. %, about 13 wt. %, about 14 wt. %, orabout 15 wt. % of dolomitic lime. In some embodiments, a met cokereplacement product comprises any combination of about 2 wt. % to about15 wt. % of dolomite, about 2 wt. % to about 15 wt. % of bentonite,about 2 wt. % to about 15 wt. % of calcium oxide, and/or about 2 wt. %to about 15 wt. % of dolomitic lime. A high-carbon biogenic reagentaccording to the present invention, when used as a met coke replacementproduct, may have a size range from about 2 cm to about 15 cm, forexample. In some embodiments, a met coke replacement product has aminimum dimension of about ¾ inches. In some embodiments, a met cokereplacement product has a maximum dimension of about 4 inches. In someembodiments, a met coke replacement product has a minimum dimension ofabout ¾ inches and a maximum dimension of about 4 inches. In someembodiments, a met coke replacement product is substantially free offossil fuel.

In some embodiments, the met coke replacement product further comprisesan additive such as chromium, nickel, manganese, magnesium oxide,silicon, aluminum, dolomite, fluorospar, calcium oxide, lime, dolomiticlime, bentonite and combinations thereof.

Some variations of the invention utilize the high-carbon biogenicreagents as coal replacement products. Any process or system using coalcan in principle be adapted to use a high-carbon biogenic reagent.

In some embodiments, a high-carbon biogenic reagent is combined with oneor more coal-based products to form a composite product having a higherrank than the coal-based product(s) and/or having fewer emissions, whenburned, than the pure coal-based product.

For example, a low-rank coal such as sub-bituminous coal may used inapplications normally calling for a higher-rank coal product, such asbituminous coal, by combining a selected amount of a high-carbonbiogenic reagent according to the present invention with the low-rankcoal product. In other embodiments, the rank of a mixed coal product(e.g., a combination of a plurality of coals of different rank) may beimproved by combining the mixed coal with some amount of high-carbonbiogenic reagent. The amount of a high-carbon biogenic reagent to bemixed with the coal product(s) may vary depending on the rank of thecoal product(s), the characteristics of the high-carbon biogenic reagent(e.g., carbon content, heat value, etc.) and the desired rank of thefinal combined product.

For example, anthracite coal is generally characterized as having atleast about 80 wt % carbon, about 0.6 wt % sulfur, about 5 wt % volatilematter, up to about 15 wt % ash, up to about 10 wt % moisture, and aheat value of about 29 MJ/kg (approximately 12,494 Btu/lb). In someembodiments, an anthracite coal replacement product is a high-carbonbiogenic reagent according to the present invention comprising at leastabout 80 wt % carbon, not more than about 0.6 wt % sulfur, not more thanabout 15 wt % ash, and a heat value of at least about 12,000 Btu/lb.

In some embodiments, a high-carbon biogenic reagent according to thepresent invention is useful as a thermal coal replacement product.Thermal coal products are generally characterized as having high sulfurlevels, high phosphorus levels, high ash content, and heat values of upto about 15,000 Btu/lb. In some embodiments, a thermal coal replacementproduct is a high-carbon biogenic reagent comprising not more than about0.5 wt % sulfur, not more than about 4 wt % ash, and a heat value of atleast about 12,000 Btu/lb.

Some variations of the invention utilize the high-carbon biogenicreagents as carbon-based coking products. Any coking process or systemmay be adapted to use high-carbon biogenic reagents to produce coke, oruse it as a coke feedstock.

In some embodiments, a high-carbon biogenic reagent according to thepresent invention is useful as a thermal coal or coke replacementproduct. For example, a thermal coal or coke replacement product mayconsist of a high-carbon biogenic reagent comprising at least about 50wt % carbon, not more than about 8 wt % ash, not more than about 0.5 wt% sulfur, and a heat value of at least about 11,000 Btu/lb. In otherembodiments, the thermal coke replacement product further comprisesabout 0.5 wt % to about 50 wt % volatile matter. The thermal coal orcoke replacement product may include about 0.4 wt % to about 15 wt %moisture.

In some embodiments, a high-carbon biogenic reagent according to thepresent invention is useful as a petroleum (pet) coke or calcine petcoke replacement product. Calcine pet coke is generally characterized ashaving at least about 66 wt % carbon, up to 4.6 wt % sulfur, up to about5.5 wt % volatile matter, up to about 19.5 wt % ash, and up to about 2wt % moisture, and is typically sized at about 3 mesh or less. In someembodiments, the calcine pet coke replacement product is a high-carbonbiogenic reagent comprising at least about 66 wt % carbon, not more thanabout 4.6 wt % sulfur, not more than about 19.5 wt % ash, not more thanabout 2 wt % moisture, and is sized at about 3 mesh or less.

In some embodiments, a high-carbon biogenic reagent according to thepresent invention is useful as a coking carbon replacement carbon (e.g.,co-fired with metallurgical coal in a coking furnace). In oneembodiment, a coking carbon replacement product is a high-carbonbiogenic reagent comprising at least about 55 wt % carbon, not more thanabout 0.5 wt % sulfur, not more than about 8 wt % non-combustiblematerial, and a heat value of at least about 11,000 Btu per pound. Insome embodiments, a coking carbon replacement product is a high-carbonbiogenic reagent comprising at least about 55 wt. % carbon, not morethan about 0.4 wt. % sulfur, not more than about 0.035 wt. %phosphorous, and a heat value of at least about 11,000 Btu per pound. Insome embodiments, the coking carbon replacement product has a minimumdimension of about ¾ inches. In some embodiments, the coking carbonreplacement product is substantially free of fossil fuel. In someembodiments, the coking carbon replacement product comprises about 0.5wt % to about 50 wt % volatile matter, and/or one or more additives.

Some variations of the invention utilize the high-carbon biogenicreagents as carbon breeze products, which typically have very fineparticle sizes such as 6 mm, 3 mm, 2 mm, 1 mm, or smaller. In someembodiments, a high-carbon biogenic reagent according to the presentinvention is useful as a coke breeze replacement product. Coke breeze isgenerally characterized as having a maximum dimension of not more thanabout 6 mm, a carbon content of at least about 80 wt %, 0.6 to 0.8 wt %sulfur, 1% to 20 wt % volatile matter, up to about 13 wt % ash, and upto about 13 wt % moisture. In some embodiments, a coke breezereplacement product is a high-carbon biogenic reagent according to thepresent invention comprising at least about 80 wt % carbon, not morethan about 0.8 wt % sulfur, not more than about 20 wt % volatile matter,not more than about 13 wt % ash, not more than about 13 wt % moisture,and a maximum dimension of about 6 mm.

In some embodiments, a high-carbon biogenic reagent according to thepresent invention is useful as a carbon breeze replacement productduring, for example, taconite pellet production or in an iron-makingprocess. In some embodiments, a carbon breeze replacement product is ahigh-carbon biogenic reagent comprising at least about 55 wt. % carbon,not more than about 0.4 wt. % sulfur, not more than about 0.035 wt. %phosphorous, and a heat value of at least about 11,000 Btu per pound. Insome embodiments, the carbon breeze replacement product has a minimumdimension of about ⅛ inches. In some embodiments, the carbon breezereplacement product is substantially free of fossil fuel.

Some variations of the invention utilize the high-carbon biogenicreagents as feedstocks for various fluidized beds, or as fluidized-bedcarbon-based feedstock replacement products. The carbon may be employedin fluidized beds for total combustion, partial oxidation, gasification,steam reforming, or the like. The carbon may be primarily converted intosyngas for various downstream uses, including production of energy(e.g., combined heat and power), or liquid fuels (e.g., methanol orFischer-Tropsch diesel fuels).

In some embodiments, a high-carbon biogenic reagent according to thepresent invention is useful as a fluidized-bed coal replacement productin, for example, fluidized bed furnaces wherever coal would be used(e.g., for process heat or energy production). In some embodiments, afluidized-bed replacement product is a high-carbon biogenic reagentcomprising at least about 55 wt. % carbon, not more than about 0.4 wt. %sulfur, not more than about 0.035 wt. % phosphorous, and a heat value ofat least about 11,000 Btu per pound. In some embodiments, thefluidized-bed replacement product has a minimum dimension of about ¼inches. In some embodiments, the fluidized-bed replacement product has amaximum dimension of about 2 inches. In some embodiments, thefluidized-bed replacement product has a minimum dimension of about ¼inches and a maximum dimension of about 2 inches. In some embodiments,the fluidized-bed replacement product is substantially free of fossilfuel.

Some variations of the invention utilize the high-carbon biogenicreagents as carbon-based furnace addition products. Coal-based carbonfurnace addition products are generally characterized as having highsulfur levels, high phosphorus levels, and high ash content, whichcontribute to degradation of the metal product and create air pollution.In some embodiments, a carbon furnace addition replacement productcomprising a high-carbon biogenic reagent comprises not more than about0.5 wt % sulfur, not more than about 4 wt % ash, not more than about0.03 wt % phosphorous, and a maximum dimension of about 7.5 cm. In someembodiments, the carbon furnace addition replacement product replacementproduct comprises about 0.5 wt % to about 50 wt % volatile matter andabout 0.4 wt % to about 15 wt % moisture. In some embodiments, thefurnace addition replacement product is a high-carbon biogenic reagentcomprising at least about 80 wt % carbon, no more than about 0.4 wt % orless sulfur, no more than about 0.035 wt % phosphorous, no more thanabout 5 wt. % of manganese, no more than about 5 wt. % of fluorospar,and a heat value of at least about 11,000 BTU/lb. In some embodiments,the furnace addition replacement product further comprises about 5 wt %to about 10 wt % of dolomite, for example about 5 wt. %, about 6 wt. %,about 7 wt. %, about 8 wt. %, about 9 wt. %, or about 10 wt. % ofdolomite. In some embodiments, the furnace addition replacement productfurther comprises about 5 wt % to about 10 wt % of dolomitic lime, forexample about 5 wt. %, about 6 wt. %, about 7 wt. %, about 8 wt. %,about 9 wt. %, or about 10 wt. % of dolomitic lime. In some embodiments,the furnace addition replacement product further comprises about 5wt %to about 10 wt % of calcium oxide, for example about 5 wt. %, about 6wt. %, about 7 wt. %, about 8 wt. %, about 9 wt. %, or about 10 wt. % ofcalcium oxide. In some embodiments, the furnace addition replacementproduct further comprises about 5 wt. % to about 10 wt. % of dolomiticlime and about 5 wt. % to about 10 wt. % of calcium oxide. In someembodiments, the furnace addition replacement product further comprisesabout 5 wt. % to about 10 wt. % of dolomite, about 5 wt. % to about 10wt. % of dolomitic lime and about 5 wt. % to about 10 wt. % calciumoxide. In some embodiments, the furnace addition replacement product hasa minimum dimension of about ¾ inches. In some embodiments, the furnaceaddition replacement product has a maximum dimension of about 2 inches.In some embodiments, the furnace addition has a minimum dimension ofabout ¾ inches and a maximum dimension of about 2 inches. In someembodiments, the furnace addition replacement product is substantiallyfree of fossil fuel

In some embodiments, a high-carbon biogenic reagent according to thepresent invention is useful as a furnace addition carbon additive at,for example, basic oxygen furnace or electric arc furnace facilitieswherever furnace addition carbon would be used. For example, furnaceaddition carbon may be added to scrap steel during steel manufacturingat electric-arc furnace facilities). For electric-arc furnaceapplications, high-purity carbon is desired so that impurities are notintroduced back into the process following earlier removal ofimpurities.

In some embodiments, a furnace addition carbon additive is a high-carbonbiogenic reagent according to the present invention comprising at leastabout 80 wt % carbon, not more than about 0.5 wt % sulfur, not more thanabout 8 wt % non-combustible material, and a heat value of at leastabout 11,000 Btu per pound. In some embodiments, the furnace additioncarbon additive further comprises up to about 5 wt % manganese, up toabout 5 wt % fluorospar, about 5 wt % to about 10 wt % dolomite, about 5wt % to about 10 wt % dolomitic lime, and/or about 5 wt % to about 10 wt% calcium oxide.

Some variations of the invention utilize the high-carbon biogenicreagents as stoker furnace carbon-based products. In some embodiments, ahigh-carbon biogenic reagent according to the present invention isuseful as a stoker coal replacement product at, for example, stokerfurnace facilities wherever coal would be used (e.g., for process heator energy production). In some embodiments, an stoker carbon replacementproduct is a high-carbon biogenic replacement comprises at least about55 wt. % carbon, no more than about 0.4% sulfur, no more than about0.035 wt. % phosphorous, and a heat value of at least about 11,000 BTUper pound. In some embodiments, the stoker carbon replacement producthas a minimum dimension of about 1 inch. In some embodiments, the stokercarbon replacement product has a maximum dimension of about 3 inches. Insome embodiments, the stoker carbon replacement product has a minimumdimension of about 1 inch and a maximum dimension of about 3 inches. Insome embodiments, the stoker carbon replacement product is substantiallyfree of fossil fuel.

Some variations of the invention utilize the high-carbon biogenicreagents as injectable (e.g., pulverized) carbon-based materials. Insome embodiments, a high-carbon biogenic reagent according to thepresent invention is useful as an injection-grade calcine pet cokereplacement product. Injection-grade calcine pet coke is generallycharacterized as having at least about 66 wt % carbon, about 0.55 toabout 3 wt % sulfur, up to about 5.5 wt % volatile matter, up to about10 wt % ash, up to about 2 wt % moisture, and is sized at about 6 Meshor less. In some embodiments, a calcine pet coke replacement product isa high-carbon biogenic reagent comprising at least about 66 wt % carbon,not more than about 3 wt % sulfur, not more than about 10 wt % ash, notmore than about 2 wt % moisture, and is sized at about 6 Mesh or less.In various embodiments, the injectable carbon is also known aspulverized carbon, pulverized carbon for injection, or PCI. In variousembodiments, the injectable carbon is used as a direct energy source, areagent or both.

In some embodiments, a high-carbon biogenic reagent according to thepresent invention is useful as an injectable carbon replacement productat, for example, basic oxygen furnace or electric arc furnace facilitiesin any application where injectable carbon would be used (e.g., injectedinto slag or ladle during steel manufacturing). In some embodiments, aninjectable carbon replacement product is a high-carbon biogenicreplacement comprises at least about 55 wt. % carbon, no more than about0.4% sulfur, no more than about 0.035 wt. % phosphorous, and a heatvalue of at least about 11,000 BTU per pound. In some embodiments, theinjectable carbon replacement product further comprises up to about 10wt. % of dolomitic lime. In some embodiments, the injectable carbonreplacement product further comprises up to about 10 wt. % of calciumoxide. In some embodiments, the injectable carbon replacement productfurther comprises up to about 10 wt. % of dolomitic lime and up to about10 wt. % of calcium oxide. In some embodiments, the injectable carbonreplacement product has a maximum dimension of about ⅛ inches. In someembodiments, the injectable carbon replacement product is substantiallyfree of fossil fuel.

In some embodiments, a high-carbon biogenic reagent according to thepresent invention is useful as a pulverized carbon replacement product,for example, wherever pulverized coal would be used (e.g., for processheat or energy production). In some embodiments, the pulverized coalreplacement product comprises up to about 10 percent calcium oxide. Insome embodiments, pulverized coal replacement product is a high-carbonbiogenic replacement comprises at least about 55 wt. % carbon, no morethan about 0.4% sulfur, and a heat value of at least about 11,000 BTUper pound. In some embodiments, the pulverized coal replacement producthas a maximum dimension of about ⅛ inches. In some embodiments, thepulverized coal replacement product is substantially free of fossilfuel.

Some variations of the invention utilize the high-carbon biogenicreagents as carbon addition product for metals production. In someembodiments, a high-carbon biogenic reagent according to the presentinvention is useful as a carbon addition product for production ofcarbon steel or another metal alloy comprising carbon. Coal-basedlate-stage carbon addition products are generally characterized ashaving high sulfur levels, high phosphorous levels, and high ashcontent, and high mercury levels which degrade metal quality andcontribute to air pollution. In some embodiments of this invention, thecarbon addition product comprises not more than about 0.5 wt % sulfur,not more than about 4 wt % ash, not more than about 0.03 wt %phosphorus, a minimum dimension of about 1 to 5 mm, and a maximumdimension of about 8 to 12 mm.

Some variations of the invention utilize the high-carbon biogenicreagents as carbon electrodes. In some embodiments, a high-carbonbiogenic reagent according to the present invention is useful as anelectrode (e.g. anode) material suitable for use, for example, inaluminum production. In some embodiments, an electrode materialcomprises a high-carbon biogenic reagent according to the presentinvention, in any embodiment. In some embodiments, a carbon electrodecomprises a high-carbon biogenic reagent comprising at least about 55wt. % carbon and no more than about 0.5 wt. % sulfur. In someembodiments, the carbon electrode is substantially free of fossil fuel.

Other uses of the high-carbon biogenic reagent in carbon electrodesinclude applications in batteries, fuel cells, capacitors, and otherenergy-storage or energy-delivery devices. For example, in a lithium-ionbattery, the high-carbon biogenic reagent may be used on the anode sideto intercalate lithium. In these applications, carbon purity and low ashcan be very important. In some embodiments, a method of manufacturing ametal comprises a step wherein a carbon electrode is consumed. In someembodiments, the carbon electrode comprises a high-carbon biogenicreagent comprising at least about 55 wt. % carbon and no more than about0.5 wt. % sulfur. In some embodiments, the carbon electrode issubstantially free of fossil fuel.

Some variations of the invention utilize the high-carbon biogenicreagents as catalyst supports. Carbon is a known catalyst support in awide range of catalyzed chemical reactions, such as mixed-alcoholsynthesis from syngas using sulfided cobalt-molybdenum metal catalystssupported on a carbon phase, or iron-based catalysts supported on carbonfor Fischer-Tropsch synthesis of higher hydrocarbons from syngas.

Some variations of the invention utilize the high-carbon biogenicreagents as activated carbon products. Activated carbon is used in awide variety of liquid and gas-phase applications, including watertreatment, air purification, solvent vapor recovery, food and beverageprocessing, and pharmaceuticals. For activated carbon, the porosity andsurface area of the material are generally important. The high-carbonbiogenic reagent provided herein may provide a superior activated carbonproduct, in various embodiments, due to (i) greater surface area thanfossil-fuel based activated carbon; (ii) carbon renewability; (iii)vascular nature of biomass feedstock in conjunction with additivesbetter allows penetration/distribution of additives that enhancepollutant control; and (iv) less inert material (ash) leads to greaterreactivity.

In some embodiments, the amounts of various components of high-carbonbiogenic reagent compositions disclosed herein are determined on a drybasis. In some embodiments, the amounts of various components ofhigh-carbon biogenic reagent compositions disclosed herein aredetermined on an ash-free basis. In some embodiments, the amounts ofvarious components of high-carbon biogenic reagent compositionsdisclosed herein are determined on a dry, ash-free basis.

It should be recognized that in the above description of marketapplications of high-carbon biogenic reagents, the describedapplications are not exclusive, nor are they exhaustive. Thus ahigh-carbon biogenic reagent that is described as being suitable for onetype of carbon product may be suitable for any other applicationdescribed, in various embodiments. These applications are exemplaryonly, and there are other applications of high-carbon biogenic reagents.In various embodiments, the injectable carbon is used as a direct energysource, as a reagent, or both.

In addition, in some embodiments, the same physical material may be usedin multiple market processes, either in an integrated way or insequence. Thus, for example, a high-carbon biogenic reagent that is usedas a carbon electrode or an activated carbon may, at the end of itsuseful life as a performance material, then be introduced to acombustion process for energy value or to a metal process, etc.

Some embodiments may employ an activated carbon both for itsreactive/adsorptive properties and also as a fuel. For example, anactivated carbon injected into an emissions stream may be suitable toremove contaminants, followed by combustion of the activated carbonparticles and possibly the contaminants, to produce energy and thermallydestroy or chemically oxidize the contaminants.

Significant environmental and product use advantages may be associatedwith high-carbon biogenic reagents, compared to conventionalfossil-fuel-based products. The high-carbon biogenic reagents may be notonly environmentally superior, but also functionally superior from aprocessing standpoint because of greater purity, for example.

With regard to metals production, production of biogenic reagents withthe disclosed process can result in significantly lower emissions of CO,CO₂, NO_(x), SO₂, and hazardous air pollutants compared to the coking ofcoal-based products necessary to prepare them for use in metalsproduction.

Use of high-carbon biogenic reagents in place of coal or coke alsosignificantly reduces environmental emissions of SO₂, hazardous airpollutants, and mercury.

Also, because of the purity of these high-carbon biogenic reagents(including low ash content), the biogenic reagents have the potential toreduce slag and increase production capacity in batch metal-makingprocesses.

EXAMPLES Example 1. Preparation of Biogenic Reagent—General Method

Wood substrate red pine large chips, Douglas fir cylinders (1.25-inchdiameter pieces) and Douglas fir pieces (approximately 2 inches by 2inches), were loaded into a loading hopper having an optionally heatednitrogen gas flow. Optionally, a 1% aqueous solution of an additive(e.g., NaOH and/or KOH) was applied by spray to the wood substrate whilein the hopper or by soaking the biomass in the aqueous additivesolution. Regardless of the application method, the additive solutionwas allowed to penetrate the biomass for 30 minutes before the biomasswas dried. Once the reactor had reached the desired temperature,rotation of the reactor was initiated and the wood substrate was fedslowly by activating the material feed system. Average residence timesin the heated portion of the reactor for each batch are indicated inTable 1. After exiting the heated portion of the reactor, the pyrolyzedmaterial collected in a discharge hopper. A conveyor removed thebiogenic reagent from the discharge hopper for further analysis.

Biogenic reagent was prepared according to the General Method aboveusing various feedstock sizes, varying reactor temperatures, heated orambient nitrogen, additive, and residence times. Table 1 summarizes thepyrolysis parameters for each batch.

TABLE 1 Preparation of Biogenic Reagent. Sam- Substrate Reactor NitrogenResidence ple Size Temp. Temp. Additive Time A Large chips 371° C.Ambient None 0.5 hours (20-25° C.) B Large chips 350° C. Ambient None0.5 hours C Large chips 350° C. 300° C. None 0.5 hours D 1.25-inch 600°C. 300° C. None 2 hours cylinders E 2 × 2 inches 600° C. 300° C. None 2hours F Large chips 480° C. Ambient None 4 hours G Large chips 480° C.Ambient KOH 4 hours H Large chips 370° C. Ambient KOH 2.5 hours I Largechips 370° C. Ambient KOH 2 hours J1 Treated N/A N/A NaOH N/A Input J2J1 Output 370° C. Ambient NaOH 2 hours

Example 2. Analysis of Biogenic Reagent

Parameters of the biogenic reagents prepared according to the GeneralMethod of Example 1 were analyzed according to Table 2 below.

TABLE 2 Methods Used to Analyze Biogenic Reagents. Parameter MethodMoisture (total) ASTM D3173 Ash content ASTM D3174 Volatile Mattercontent ASTM D3175 Fixed Carbon content ASTM D3172 (by calculation)Sulfur content ASTM D3177 Heating Value ASTM D5865 (BTU per pound)Carbon content ASTM D5373 Hydrogen content ASTM D5373 Nitrogen contentASTM D5373 Oxygen content ASTM D3176 (by calculation)

Results for Samples A through F, which were prepared without the use ofadditives, are shown in Table 3 below.

TABLE 3 Characteristics of Biogenic Reagents A Through F. Sample → A B CD E F Moisture 2.42 3.02 3.51 0.478 0.864 4.25 (wt. %) Ash (wt. %) 1.160.917 0.839 1.03 1.06 1.43 Volatile 38.7 46.4 42.8 2.8 17.0 18.4 Matter(wt. %) Fixed 57.7 49.4 52.9 95.7 81.0 76.0 Carbon (wt. %) Sulfur ND^(†)ND ND ND ND ND (wt. %) Heat Value 12,807 12,452 12,346 14,700 13,98313,313 (BTU/lb.) Carbon 73.3 71.2 71.0 NT^(‡) NT 84.1 (wt. %) Hydrogen4.47 4.85 4.63 NT NT 2.78 (wt. %) Nitrogen 0.251 0.227 0.353 NT NT 0.259(wt. %) Oxygen 18.3 19.7 19.6 NT NT 7.13 (wt. %) ^(†)ND: less than 0.05wt. % sulfur content. ^(‡)NT: Not Tested.

Results for Samples G through J2, which were prepared with the use ofadditives, are shown in Table 4 below.

TABLE 4 Characteristics of Biogenic Reagents G Through J2. Sample → G HI J1 J2 Moisture (wt. %) 3.78 5.43 1.71 15.2 4.05 Ash (wt. %) 5.97 12.615.8 7.9 20.2 Volatile Matter 17.8 30.2 19.7 59.1 25.3 (wt. %) FixedCarbon 72.5 51.7 62.8 17.8 50.5 (wt. %) Sulfur (wt. %) ND^(†) ND ND NDND Heat Value 12,936 10,530 11,997 6,968 9,639 (BTU/lb.) Carbon (wt. %)81.1 64.4 69.6 41.9 67.2 Hydrogen (wt. %) 2.6 3.73 3.82 4.64 3.78Nitrogen (wt. %) 0.20 0.144 0.155 0.145 0.110 Oxygen (wt. %) 6.31 13.68.91 30.2 4.6 ^(†)ND: less than 0.05 wt. % sulfur content.

Example 3. Production of a High Heat Value Biogenic Reagent

This example demonstrates production of a biogenic reagent having a highheat value.

A feedstock comprising Douglas fir cylindrical pieces (1⅛″ diameter,approx. 1.5-inch lengths) was pyrolyzed according to the General Methodof Example 1. The reactor was heated to 600° C. and the feedstock waspyrolyzed with a residence time of 30 minutes. After cooling, theresulting biogenic reagent was analyzed according to the methodsdescribed in Example 2. Results are shown in Table 5.

TABLE 5 Analysis of High Heat Value Biogenic Reagent. ASTM Ash &Parameter Method As-Received Moisture Free Moisture Free ProximateAnalysis Moisture (total) D3173 1.45 wt. % — — Ash D3174 0.829 wt. %0.841 wt. % — Volatile Matter D3175 7.15 wt. % 7.26 wt. % 7.32 wt. %Fixed Carbon D3172 90.6 wt. % 91.9 wt. % 92.7 wt % Sulfur D3177 ND^(†)ND ND Heat Value D5865 14,942 BTU/lb 15,162 BTU/lb 15,291 BTU/lbUltimate Analysis Moisture (total) D3173 1.45 wt. % — — Ash D3174 0.829wt. % 0.841 wt. % — Sulfur D3177 ND ND ND Carbon D5373 88.3 wt. % 89.6wt. % 90.4 wt. % Hydrogen^(‡) D5373 1.97 wt. % 2.00 wt. % 2.01 wt. %Nitrogen D5373 0.209 wt. % 0.212 wt. % 0.214 wt. % Oxygen^(‡) D3176 7.19wt. % 7.30 wt. % 7.36 wt. % ^(†)ND: Sulfur content was less than 0.050wt. % (as-received), less than 0.051 wt. % (moisture-free), or less than0.052 wt. % (ash and moisture-free). ^(‡)Excluding water.

Example 4. Production of a High Heat Value Biogenic Reagent

This example demonstrates production of a biogenic reagent having a highheat value.

A feedstock comprising red pine chips having an average particle size ofapproximately 1-inch by ½ inches by ⅛ inches was pyrolyzed according tothe General Method of Example 1. The reactor was heated to 550° C. andthe feedstock was pyrolyzed with a residence time of 30 minutes. Aftercooling, the resulting biogenic reagent was analyzed according to themethods described in Example 2. Results are shown in Table 6.

TABLE 6 Analysis of High Heat Value Biogenic Reagent. ASTM Ash &Parameter Method As-Received Moisture Free Moisture Free ProximateAnalysis Moisture (total) D3173 2.55 wt. % — — Ash D3174 1.52 wt. % 1.56wt. % — Volatile Matter D3175 10.1 wt. % 10.4 wt. % 10.5 wt. % FixedCarbon D3172 85.8 wt. % 88.1 wt. % 89.5 wt % Sulfur D3177 ND^(†) ND NDHeat Value D5865 14,792 BTU/lb 15,179 BTU/lb 15,420 BTU/lb UltimateAnalysis Moisture (total) D3173 2.55 wt. % — — Ash D3174 1.52 wt. % 1.56wt. % — Sulfur D3177 ND ND ND Carbon D5373 88.9 wt. % 91.2 wt. % 92.7wt. % Hydrogen^(‡) D5373 2.36 wt. % 2.42 wt. % 2.45 wt. % Nitrogen D53730.400 wt. % 0.410 wt. % 0.417 wt. % Oxygen^(‡) D3176 4.22 wt. % 4.33 wt.% 4.40 wt. % ^(†)ND: Sulfur content was less than 0.050 wt. %(as-received), less than 0.051 wt. % (moisture-free), or less than 0.052wt. % (ash and moisture-free). ^(‡)Excluding water.

Example 5. Production of a Biogenic Coke Replacement Product forBlending with Met Coke

Biogenic reagent was prepared from milled kiln-dried wood dowelingsubstantially according to the General Method of Example 1.

Blends of met coke (Sample ID No. SGS/427-1104014-001) with 2% and 5% ofthe biogenic reagent were prepared by mixing the met coke with theappropriate amount of biogenic coke replacement product. Strength andreactivity values were measured according to ASTM D5341 for the blendscompared to met coke alone are shown in Table 7 (values are the averageof a minimum of two tests per sample).

TABLE 7 CSR and CRI of Biogenic Reagent-Met Coke Blends. Amount ofBiogenic Reagent CRI CSR 0 wt. % (baseline) 24.5% 62.8% 2 wt. % 25.7%62.3% (+1.2%) (−0.5%) 5 wt. % 28.0% 61.2% (+3.5%) (−1.6%)

This example demonstrates that a biogenic reagent prepared according tothe General Method of Example 1, when blended with met coke at 2 wt. %and 5 wt. %, is capable of achieving CRI values below 30% and CSR valuesabove 60%, corresponding with typical specifications for met coke use inlarge blast furnaces.

Example 6. Production of an Enhanced Hot-Strength Biogenic CokeReplacement Product

Red pine wood chips approximately sized 1″×½″×⅛″ were pyrolyzedaccording to the General Method of Example 1 at 600° C. with a residencetime of 30 minutes. The resulting biogenic reagent is referred to as“Sample A.”

Milled, kiln-dried wood doweling having a 1⅛″ diameter was cut intosegments having a length of about 1.5 inches each. The segments werepyrolyzed according to the General Method of Example 1 at 600° C. with aresidence time of 2 hours. The resulting biogenic reagent is referred toas “Sample B.”

Samples A and B were each placed separately into quartz tubes and heatedat 1,100° C. in the presence of CO₂ gas for one hour. After one hour,Sample A had a CSR value of about 0%. After one hour, Sample B had a CSRvalue of 64.6%. These results indicate that potential for increasing hotstrength of a biogenic coke replacement product and suitability for useas a replacement for met coke in various metal production applications.

Example 7. Preparation of Particularly Dimensioned Biogenic Reagent

As shown in Table 8 below, Biogenic Reagent having a particular shapeand average dimension was produced according to the General Method ofExample 1.

TABLE 8 Properties of Particularly Dimensioned Biogenic Reagent. FixedInitial Final Volume Initial Final Mass Sample Carbon Volume VolumeChange Mass Mass Change Blocks 90 wt. % 3.15 in³ 1.51 in³ −52% 22.77 g4.91 g −78% Cylin- 80 wt. % 1.46 in³ 0.64 in³ −56% 14.47 g 3.61 g −75%ders-1 Cylin- 90 wt. % 1.46 in³ 0.58 in³ −60% 14.47 g 3.60 g −75% ders-2

Example 8. Effect of Residence Time on Fixed Carbon Levels

The effect of residence time on fixed carbon levels in the biogenicreagent was investigated by dividing one batch of feedstock into fourgroups of approximately equal mass composed of pieces of feedstock ofapproximately equal particle size. Each of the four groups was subjectedto pyrolysis according to the General Method of Example 1 at 350° C.with residence times of 0 minutes, 30 minutes, 60 minutes, and 120minutes, respectively. Fixed carbon content of each sample wasdetermined by ASTM D3172. Results are shown in Table 9 and correspondingFIG. 14.

TABLE 9 Effect of Residence Time on Fixed Carbon Levels. SampleResidence Time Fixed Carbon Residence-1  0 minutes 17 wt. % Residence-2 30 minutes 50 wt. % Residence-3  60 minutes 66 wt. % Residence-4 120minutes 72 wt. %

Example 9. Effect of Pyrolysis Temperature on Fixed Carbon Levels

The effect of pyrolysis temperature on fixed carbon levels in thebiogenic reagent was investigated by dividing one batch of feedstockinto five groups of approximately equal mass composed of pieces offeedstock of approximately equal particle size. Each of the five groupswas subjected to pyrolysis according to the General Method of Example 1with a 30 minute residence time. Fixed carbon content of each sample wasdetermined by ASTM D3172. Results are shown in Table 10 andcorresponding FIG. 15.

TABLE 10 Effect of Residence Time on Fixed Carbon Levels. SamplePyrolysis Temp. Fixed Carbon Temperature-1 310° C. 38 wt. %Temperature-2 370° C. 58 wt. % Temperature-3 400° C. 64 wt. %Temperature-4 500° C. 77 wt. % Temperature-5 600° C. 83 wt. %

Example 10. Effect of Feedstock Particle Size on Fixed Carbon Levels

The effect of feedstock particle size on fixed carbon levels in thebiogenic reagent was investigated by pyrolyzing three groups of red pinebiomass: sawdust (average particle size of approximately 0.0625 inches),chips (average particle size of approximately 1 inch by ½ inch by ⅛inches), and chunks (cylinders having a 1⅛″ diameter and a length ofapproximately 1.5 inches). Each of the three groups was subjected topyrolysis according to the General Method of Example 1 at 400° C. for 30minutes. Fixed carbon content of each sample was determined by ASTMD3172. Results are shown in Table 11 and corresponding FIG. 16.

TABLE 11 Effect of Residence Time on Fixed Carbon Levels. Sample AverageParticle Size Fixed Carbon Sawdust ~0.0625 inches 71 wt. % Chips ~1 inch× ½ inch × 64 wt. % ⅛ inch Chunks ~1.5″ lengths of 1⅛″ 62 wt. % diametercylinders

Example 11. Effect of Oxygen Level During Pyrolysis on Mass Yield ofBiogenic Reagent

This example demonstrates the effect of oxygen levels on the mass yieldof biogenic reagent.

Two samples of hardwood sawdust (4.0 g) were each placed in a quartztube. The quartz tube was then placed into a tube furnace (LindbergModel 55035). The gas flow was set to 2,000 ccm. One sample was exposedto 100% nitrogen atmosphere, while the other sample was subjected to agas flow comprising 96% nitrogen and 4% oxygen. The furnace temperaturewas set to 290° C. Upon reaching 290° C. (approximately 20 minutes), thetemperature was held at 290° C. for 10 minutes, at which time the heatsource was shut off, and the tube and furnace allowed to cool for 10minutes. The tubes were removed from the furnace (gas still flowing at2,000 ccm). Once the tubes and samples were cool enough to process, thegases were shut off, and the pyrolyzed material removed and weighed(Table 12).

TABLE 12 Effect of Oxygen Levels During Pyrolysis on Mass Yield. SampleAtmosphere Mass Yield Atmosphere-1(a) 100% Nitrogen 87.5%Atmosphere-2(a) 96% Nitrogen, 50.0% 4% Oxygen

Example 12. Effect of Oxygen Level During Pyrolysis on Fixed ContentLevel and Heat Value of Biogenic Reagent

The increase in fixed carbon content and heat value from the use of aCarbon Recovery Unit (“CRU”) is demonstrated.

Pyrolysis of hardwood sawdust according to Example 10 was performed. Astandard coconut shell charcoal (“CSC”) tube (SKC Cat. No. 226-09) wasplaced in the off-gas stream following a standard midget impingercontaining 10 mL of HPLC-grade water. Increases in fixed carbon levelsand heat value were compared to a CSC tube that had not been exposed toany off-gases (Table 13, ash and moisture-free data).

TABLE 13 Increase in Fixed Carbon Content and Heat Value as a Functionof Oxygen Content During Pyrolysis. Increase in Carbon Increase inSample Atmosphere Content Heat Value Atmosphere-1(b) 100% Nitrogen +3.2%+567 BTU/lb (+4.0%) Atmosphere-2(b) 96% Nitrogen, +1.6% +928 BTU/lb 4%Oxygen (+6.5%)

The results of Examples 11 and 12 demonstrate the benefits ofmaintaining a near-zero oxygen atmosphere to on mass yield andcommercial value of the disclosed pyrolyzation process. Using theoff-gases from these two experiments it was also possible to demonstratethat the BTU-laden gases exiting the process can be captured for thepurpose of enhancing the BTU content and/or carbon content, of a carbonsubstrate (coal, coke, activated carbon, carbon).

Example 13. Effect of Heated Nitrogen on Fixed Carbon Content of aBiogenic Reagent

This example demonstrates the effect of introducing heated nitrogen gasto the biomass processing unit.

Production of biogenic reagent using a biomass consisting of red pinewood chips having a typical dimension of 1 inch by ½ inches by ⅛ incheswas performed according to the General Method of Example 1 with afour-zone heat pilot-scale reactor at 350° C. In the first run, nitrogenwas introduced at ambient temperature. In a second run, which wasperformed immediately after the first run in order to minimize variationin other parameters, nitrogen was preheated to 300° C. before injectioninto the pyrolysis zone. In each case, the nitrogen flow rate was 1.2cubic feet per minute, and the biomass was processed for 30 minutes.

Fixed carbon content was measured on a dry, ash-free basis according toASTM D3172 for each run (Table 14).

TABLE 14 Effect of Nitrogen Temperature on Fixed Carbon Content of aBiogenic Reagent. Nitrogen Fixed Carbon Sample Temperature ContentAtmosphere-1(c) Ambient 51.7% Atmosphere-2(c) 300° C. 55.3%

These test results demonstrate a 7.0% increase[(100)(55.3%−51.7%)/55.3%] in the fixed carbon content of the biogenicreagent carbonized product by utilizing pre-heated nitrogen.

Example 14. Improvement of Mass Yield by Pretreatment of Biomass

This example demonstrates the production of a biogenic activated carbonproduct having an additive, namely iron(II) bromide.

An aqueous solution of iron(II) bromide hydrate was created by mixing72.6 grams of iron(II) bromide hydrate into 1 gallon of water (e.g.,1.0% bromine aqueous solution). This solution was added to 5.23 pounds(2.37 kg) of air-dried (12% moisture content) red pine wood chips. Eachwood chip was approximately 1″×½″×⅛″.

The container of wood chips and solution was sealed with a water tightlid. The contents were mixed periodically over the course ofapproximately four hours by tipping and rolling the container andcontents. The wood chips and solution were kept sealed overnight toallow for saturation of the wood chips with the solution.

Thereafter, the contents were transferred to an open water-proof tub andallowed to air dry for several hours, with periodic mixing until allfree liquid had been absorbed by the wood chips or evaporated. Thecontents were transferred to an air-dryer and allowed to dry overnight.

The pretreated, air-dried wood chips were verified to have 12% moisturecontent. The mass of the pretreated, air dried wood chips was determinedto be 5.25 lbs (2.38 kg). The contents were transferred to a pyrolysisreactor with nitrogen gas preheated to 300° C. with a gas flow rate of0.4 cubic feet per minute. Pyrolysis occurred at 370° C. for 30 minutes

The finished product was removed from the reactor at a temperature ofless than 100° C. Upon reaching room temperature (approximately 23° C.),the finished product had a mass of 2.5 pounds (1.14 kg), indicating amass yield of 47.6% based upon feedstock mass (e.g., the masscontribution of the pretreatment additive was subtracted) at 12%moisture content. On a dry basis (correcting out the 12% moisture andthe mass contribution of the pretreatment additive), the mass yield was54.1%. As shown in Table 15 below, this represents an increase of 8-15%in mass yield over untreated wood chips processed under the sameconditions.

Table 15. Pretreatment of Biomass with 1.0% Aqueous Iron(II) BromideIncreases

Mass Yield Mass Yield Pretreatment (12% Moisture) (Dry Basis) None 34.3%39.0% None 35.4% 40.2% None 37.2% 42.2% Average 35.6% 40.5% (NoPretreatment) Iron(II) Bromide 47.6% 54.1% DIFFERENCE 12.0% 13.6%

These data indicate a significant improvement in the mass yield for woodchips treated with an iron (II) bromide solution prior to pyrolyticprocessing.

In this detailed description, reference has been made to multipleembodiments of the invention and non-limiting examples relating to howthe invention can be understood and practiced. Other embodiments that donot provide all of the features and advantages set forth herein may beutilized, without departing from the spirit and scope of the presentinvention. This invention incorporates routine experimentation andoptimization of the methods and systems described herein. Suchmodifications and variations are considered to be within the scope ofthe invention defined by the claims.

All publications, patents, and patent applications cited in thisspecification are herein incorporated by reference in their entirety asif each publication, patent, or patent application were specifically andindividually put forth herein.

Where methods and steps described above indicate certain eventsoccurring in certain order, those of ordinary skill in the art willrecognize that the ordering of certain steps may be modified and thatsuch modifications are in accordance with the variations of theinvention. Additionally, certain of the steps may be performedconcurrently in a parallel process when possible, as well as performedsequentially.

Therefore, to the extent there are variations of the invention, whichare within the spirit of the disclosure or equivalent to the inventionsfound in the appended claims, it is the intent that this patent willcover those variations as well. The present invention shall only belimited by what is claimed.

I/We claim:
 1. A biogenic stoker carbon composition comprising, on a drybasis: at least about 55 wt % total carbon; at most about 5 wt %hydrogen; at most about 1 wt % nitrogen; at most about 0.5 wt %phosphorus; at most about 0.2 wt % sulfur; and an additive selected froma metal, a metal oxide, a metal hydroxide, a metal halide, or acombination thereof.
 2. The biogenic stoker carbon composition of claim1, wherein the additive is selected from magnesium, manganese, aluminum,nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus,tungsten, vanadium, iron halide, iron chloride, iron bromide, magnesiumoxide, dolomite, dolomitic lime, fluorite, fluorospar, bentonite,calcium oxide, lime, or a combination thereof.
 3. The biogenic stokercarbon composition of claim 1, wherein the biogenic stoker carboncomposition comprises at least about 70 wt % total carbon on a drybasis.
 4. The biogenic stoker carbon composition of claim 1, wherein thebiogenic stoker carbon composition comprises at least about 95 wt %total carbon on a dry basis.
 5. The biogenic stoker carbon compositionof claim 1, wherein the biogenic stoker carbon composition issubstantially free of fossil fuel.
 6. The biogenic stoker carboncomposition of claim 1, wherein the total carbon consists essentially ofbiogenic carbon.
 7. The biogenic stoker carbon composition of claim 1,comprising a heat value of at least about 11,000 BTU per pound.
 8. Thebiogenic stoker carbon composition of claim 1, comprising a minimumdimension of about 1 inch and a maximum dimension of about 3 inches. 9.A biogenic stoker carbon composition comprising, on a dry basis: atleast about 55 wt % total carbon; at most about 5 wt % hydrogen; at mostabout 1 wt % nitrogen; at most about 0.5 wt % phosphorus; at most about0.2 wt % sulfur; and an additive selected from an acid or a saltthereof, or a base or a salt thereof.
 10. The biogenic stoker carboncomposition of claim 9, wherein the additive is selected from sodiumhydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide,hydrogen chloride, sodium silicate, potassium permanganate, or acombination thereof.
 11. The biogenic stoker carbon composition of claim9, wherein the biogenic stoker carbon composition comprises at leastabout 70 wt % total carbon on a dry basis.
 12. The biogenic stokercarbon composition of claim 9, wherein the biogenic stoker carboncomposition comprises at least about 95 wt % total carbon on a drybasis.
 13. The biogenic stoker carbon composition of claim 9, whereinthe biogenic stoker carbon composition is substantially free of fossilfuel.
 14. The biogenic stoker carbon composition of claim 9, wherein thetotal carbon consists essentially of biogenic carbon.
 15. The biogenicstoker carbon composition of claim 9, comprising a heat value of atleast about 11,000 BTU per pound.
 16. The biogenic stoker carboncomposition of claim 9, comprising a minimum dimension of about 1 inchand a maximum dimension of about 3 inches.
 17. A biogenic stoker carboncomposition consisting essentially of, on a dry basis, carbon, hydrogen,oxygen, nitrogen, phosphorus, sulfur, non-combustible matter, and anadditive selected from the group consisting of magnesium, manganese,aluminum, nickel, chromium, silicon, boron, cerium, molybdenum,phosphorus, tungsten, vanadium, iron halide, iron chloride, ironbromide, magnesium oxide, dolomite, dolomitic lime, fluorite,fluorospar, bentonite, calcium oxide, lime, and combinations thereof.18. A biogenic stoker carbon composition consisting essentially of, on adry basis, carbon, hydrogen, nitrogen, phosphorus, sulfur,non-combustible matter, and an additive selected from the groupconsisting of sodium hydroxide, potassium hydroxide, magnesium oxide,hydrogen bromide, hydrogen chloride, sodium silicate, potassiumpermanganate, and combinations thereof.